Daniil Medvedev, the world number two, can seal the title for Russia in Madrid with a victory over Marin Cilic while the former US Open champion will be hoping to extend Croatia’s chances into the doubles.
The 23-year-old Gojo has been instrumental in Croatia reaching the final after winning all three of his previous singles matches but, ranked 279th in the world, he was always going to be up against it versus fifth-ranked Rublev.
The Russian’s precision from the baseline ultimately prevailed but Gojo pushed him all the way, particularly in the second set, when the Croatian led 5-4 in the tie-break.
The pivotal moment in the first came halfway through as two Gojo backhands into the net gave Rublev a pair of break points before a deep forehand forced the decisive Gojo error.
Rublev served out with an ace and then put Gojo under pressure early in the second set but was unable to convert into a break.
After weathering the storm, Gojo held more comfortably but Rublev came again at 5-5. He took Gojo to deuce but the Croatian pinged a serve down the middle to survive.
Rublev quickly confirmed the tie-break and was gifted the first point when Gojo served a double fault.
Gojo won it back when a Rublev forehand popped up off his frame but he then opted to leave a Rublev pass, which plopped onto the line.
Gojo was in sight of a decider when Rublev blew a forehand wide and a pin-point serve out wide put him 5-4 in front.
But Rublev dug deep, a superb pass and a inside-out forehand winner opening up two match points. Rublev converted the first when a Gojo backhand drifted long.