The Englishmen, who only teamed up at the start of 2025, were the better pair in the opening set.
A poor service game from Zeballos handed Salisbury and Skupski a break at 5-3 before Liverpudlian Skupski served it out.
They looked on track to get the job done in two sets and exact some revenge for July’s defeat in Paris when leading 0-40 at 3-3 in the second – but Granollers stood firm and went on to hold.
After winning 15 successive points on serve, Salisbury faltered in the second set tie-break – dropping serve twice – to send the match to a decider.
Salisbury and Skupski did not have to defend a break point until the third set and showed resilience to stave them off initially.
Salisbury and Skupski led 5-4 when they found themselves with three championship points on their opponents’ serve, but a series of poor returns cost them.
Roles were reversed in the next game as Skupski was broken before Granollers served out victory.