Kvitova hit 43 winners to Muguruza's 21 with the Spaniard winning 67 percent of her first serve points to the Czech's 65 in their two-hour, 38 minute battle,
Story of the match
After five routine holds to start the match, Kvitova broke following a couple of erratic shots by Muguruza and the Czech fired a winner into the open court to take a 4-2 lead.
The Spaniard broke back thanks to Kvitova double-faulting and a hold brought her level at 4-4. Another double fault by the 21st seed a few games later put Muguruza in front 6-5.
She was able to serve out the set and on set point, Kvitova found the net with a backhand to put Muguruza up a set.
The second set started much like the first with both players comfortably holding until Kvitova broke in the sixth game and consolidated her lead to extend her advantage to 5-2.
A two-time quarterfinalist in New York, Kvitova served out the set, firing an ace to wrap it up and force a third and deciding set in this power-hitting thriller.
Muguruza broke in the sixth game following a forehand error by the Czech to take control of the deciding set by a 4-2 scoreline and a hold made it 5-2, the ninth seed a game away from victory.
Two games later, the Spaniard stepped up to serve for the match, but started with a double fault, was lured into error by Kvitova's sudden strategic use of the slice, and was broken on a forehand shank.
Muguruza had two match points at 6-5, but Kvitova saved the first with an ace and the second when the Spaniard netted a forehand and she eventually held in a ten-minute game.
A ten-point tiebreaker would decide this epic and minibreaks were exchanged midway through. Kvitova took control, winning four of the next five points to go in front 8-5.
Muguruza fought back and staved off three match points, but Kvitova hit a spectacular running forehand to set up a fourth to make the score 11-10 and a point later, one final forehand error by the Spaniard ended an instant classic.