Murray, the 2009 champion in Rotterdam, recorded a 2-6, 7-6 (2), 6-3 over Robin Haase while Rublev got past qualifier Marcos Giron 7-6 (1), 6-3 to begin his tournament.
This is the second career meeting between Murray and Rublev with the Brit winning their only previous encounter 6-3, 6-0, 6-2 in the second round of the 2017 Australian Open.
The match will lead off the night session on Centre Court with the winner advancing to the quarterfinals against sixth seed David Goffin or French qualifier Jeremy Chardy.
This is a matchup of contrasting styles as Murray will look to play long points from the baseline, trying to dictate with his backhand while Rublev will want to overpower the Brit, playing short points and using his forehand to great effect.
The Russian will look to attack the Murray second serve, but also has to guard against overhitting, something he's been guilty of in the past. Having not played in almost four years means that match in Melbourne shouldn't be indicative of anything that will occur here.
Murray showed plenty of fighting spirit against Haase and could use his experience in these blockbuster matches while Rublev has the confidence of having won 16 consecutive matches at the 500 level dating back to last year.
This is a match Rublev should win. He's in tremendous form, looks like he has gotten his powerful game under control and with the draw opening up, is now one of the favorites to claim the title.
With all of that being said, it would be unwise to count Murray out. If he can make this a long three-setter, he could force errors out of the fourth seed in pressure moments.
While I think we will eventually see the three-time major champion close to his best in the future and the signs were encouraging in his last match, asking him to beat an in-form Rublev is probably too much at this stage.
Prediction: Andrey Rublev in straight sets