Venezuela strode to a famous, shock victory over a Colombia side full of star names thanks to a Salomon Rondon header in the 60th minute.
La Vinotinto looked the deserved winners by the end of the game despite last ditch efforts from a frustrated James Rodriguez.
Throughout they defended superbly, created chances patiently and eventually took one of them ruthlessly.
Meanwhile, Colombia looked a shadow of the team that have been unbeaten since September.
The Venezuela players kneeled down in shock while some ran over to the star names in the Colombia side to swap shirts to remember a momentous occasion for the players and the country.
High fives were all around the side who masterminded a first win in their first 2015 Group C Copa America game thanks to Rondon's header, created by Juan Arango and Alejandro Guerra.
Venezuela got the game underway, sharp shadows on the floor next to them as the sun shone brightly on the Chilean pitch.
Radamel Falcao was almost in on goal within the first minute as a looping, direct ball came from midfield but he was instantly surrounded by an energetic Venezuela defence and lost the ball.
The high paced start continued after the early Falcao chance, with the huge sea of yellow in all four stands supporting Colombia on.
James Rodriguez took a first time, outside of the boot shot with his left foot from a Colombia corner but it was deflected out for a corner. The signs of early dominance from Los Cafeteros were obvious, yet they couldn't produce anything from the set piece.
Colombia start strongly
Juan Cuadrado, starting on the left flank, looked in good form from the start, dribbling in and out of two players at seven minutes. There was no goal to finish it but after months out of action at Chelsea following his January move, he still looked full of flair and energy.
While Colombia looked more ruthless on the ball, Venezuela still retained confidence that everyone knew would be needed for an upset against Jose Pekerman's side.
A strong challenge on Falcao saw James whip in a poor free-kick, right onto the head of the Venezuela defender, with the ball eventually ending back at David Ospina in goal.
Yet the ball quickly came back upfield, Falcao and Carlos Bacca - starting despite Pekerman's initial starting line up including Teo Gutierrez not the Sevilla forward - working well together as a pair in attack.
At fifteen minutes, it was the Colombian fanbase, filling the Estadio El Teniente, who were impressing most as Los Cafeteros failed to make an incisive attack in the opening stages.
Ospina winced as he took a goal kick, having gone down for a prolonged amount of time as Salamon Rondon broke away from the possession-based game to penetrate the Colombian defence.
Sejias earned a booking for Colombia, just eighteen minutes into the game.
Cuadrado drove forward and unleashed a classic, drilled cross at hip level but Baroja claimed it nervously before booting clear.
Alejandro Guerro did well to stay on the ball, driving across the pitch, moving forward patiently but Zuniga followed him all the way and clear the ball.
Venezuela confident despite being underdogs
Fernando Amorebieta earned the second booking of the game with 15 minutes to go as he arrived seconds late on Cuadrado, who crumpled on the floor.
It seemed to be a turning point in the game as a naughty kick out came Cuadrado's way, but it was only the TV cameras that caught the incident.
While Colombia looked more and more nervous as Venezuela put more and more pressure on them as they sat on the ball, La Vinotinto forced Ospina into a great save.
Juan Arango, never seeming to get any older, held off his marker well on the edge of the box before feeding in Vargas who was stopped by a massively outstretching Ospina.
Falcao found the ball at his chest as the Venezuelan defence mixed up communications and he tried an audacious chip from very close to the goal, but with no surprise it hit the top of the netting.
Arango looked to deliver Rondon a nicely weighted cross but it scooped just too far for the Venezuelan and instead it bounced into the arms of Ospina, perplexed by its bounce.
Pablo Armero, not initially starting but a late addition to the starting eleven, finally got into the penalty area - as often seen in a Colombia shirt - after 35 minutes of trying.
He charged forward, skipping through two players before looking for a penalty. Colombia then earned a free-kick but once more, James wasted the opportunity as the pattern of the star men in yellow not performing to the highest standards continued.
Meanwhile, the game continued to have a stop and start feel to it as free-kicks were constantly awarded, with both sides frustrated at the lack of chances made.
Carlos Bacca finally used his strength to power his way through the Venezuela half on the counter attack. He lost the ball initially but Pekerman's side regained possession and James' cross dribbled across the area, waiting for someone to pounce.
Colombia disappointing in first half
Falcao, James, Cuadrado, Bacca all failed to produce something special. It was Alejandro Guerra who looked to make the difference with some individual magic. With wonderful technique he latched on to a medium height ball, pulled it back over his head and volleyed it goalwards.
Ospina tipped it wide and Venezuela wasted the corner but going into the half time break, Sanvicente's side looked on the up in terms of attack.
Abel Aguilar and Fredy Guarin were hugely missed in midfield for Colombia as James Rodriguez rushed down the tunnel for half time, knowing he had to improve. There was no link in between their electric attack and quick fullbacks, leaving numbers of chances low.
Carlos Sanchez had a long range effort following a Juan Cuadrado free-kick but it squeezed wide of the post at the start of the second half.
The first five minutes after the restart failed to show a difference in Colombia's drab first half play that lacked any of the normal flow seen by Pekerman's side.
Yet the tempo improved of their play as Zuniga looked to whip a cross in after another corner was wasted.
They produced a spectacular opportunity as Zuniga's throw was flicked on with a volleyed backheel by Falcao for James to volley, deflected wide for a corner.
Rondon climbed well above Murillo but the referee blew his whistle for a foul as he headed towards Ospina's goal. No matter what Colombia did to up the tempo, Venezuela's energy and aggresiveness continued to reap rewards.
Edwin Valencia was ready to pounce as Falcao knocked down James' free-kick, better than the previous wasted chances, but he was clearly offside and Venezuela attacked quickly.
That chance came to nothing for Salomon Rondon, but moments later he made up for it.
Salomon Rondon provides Venezuela with winning goal
As Juan Arango stormed forward, he delivered a delightful ball to Guerra who produced something of similar quality to give Rondon the chance to head past Ospina.
That, Rondon did and ran off in ecstasy as they finally got the biggest reward for the biggest of efforts.
Jose Pekerman responded instantly as he looked to alter the balance of the game, bringing on Edwin Cardona for Carlos Sanchez in an attacking substitution.
Yet the game did not alter, and the game to did turn in favour of his team. Venezuela expanded on their advantage, beginning to pound Ospina's area with chances, winning every 50-50 challenge and making it count.
Vargas and Guerro combined with Arango and Rondon to produce some great attacks and while the clear chances didn't come quickly, they looked in the ascendensy, despite having just scored they never sat back.
Teo Gutierrez finally came on for Colombia, replacing the quiet Carlos Bacca. His name was shouted in joy by the Colombians in Chile who could see the impact that he could make, his work rate and willingness to drop deep for the side, unlike Bacca.
He got an early chance after coming on, receiving the ball under his feet from a tight angle before it was clear away with a hoof from Venezeula.
Lucena got his name in the book for timewasting as Jose Pekerman continued to shout from the touchline in frustrating.
His efforts from his technical area were rewarded as James struck from distance beautifully with his left foot, Cardona struck powerfully from a bit closer before Zapata failed to convert from close range from the resulting corner.
The noise levels increased hugely as Colombia finally tested Baroja, the yellow walls in the stands rising to their feet, the big names in the side finally providing some individual moments of magic.
Jackson Martinez came on to join Radamel Falcao and Teo Gutierrez upfront, coming on for the full back Pablo Armero.
Juan Cuadrado slotted in at right-back as Venezuela felt the full force of Colombia's incredible depth in attack, now with three strikers in Pekerman's side.
Edwin Cardona had an opportunity from a free-kick but it never looked like troubling Baroja, with little pace on the ball and no movement.
Jackson was involved straight away, setting up Cuadrado for an absolutely incredible effort of an overhead kick, but it snuck wide of the left post.
Juan Arango came off to great applause from the small numbers of Venezuela fans, happy to the 35-year-old put in another brilliant performance.
Whatever Colombia tried, Venezuela prevented as defence became the only thing on their minds, with just minutes to go for a famous win against the stars of Colombia.
Gonzalez broke free for Venezuela as the game moved into five minutes of stoppage time but his cross was dealt with calmly.
James put in a poor cross for Barajo to deal with easily and bowed his head in frustration as nothing went his way with little time to go.
Venezuela beat Colombia, shock result
The final whistle blew to the sheer delight of a close knit Venezuela side who played with passion, concentration and determination to mastermind a vital win over Colombia.
Colombia need a win against Brazil to get their Copa America campaign underway properly after a hugely disappointing performance on Sunday evening.
Meanwhile, Venezuela will be celebrating massively given the unexpected nature of this win. Players knelt in shock, others ran over the Falcao and James to swap shirts.
Yet those stars couldn't change the game for Colombia, who are behind Venezuela, the side with a shock chance of progressing from the group stage thanks to this win.