Novak won his third Rome Masters crown when he beat Rafael Nadal 4-6, 6-3, 6-3 in the finals on Sunday.
Novak will meet the defending champion and top seed Rafael Nadal for the championship trophy.
Nole beat no.5 seed David Ferrer 7-5, 4-6, 6-3 to advance into the Internazionali BNL d’Italia last four.
Novak came back from a set down to beat Philipp Kohlschreiber 4-6, 6-2, 6-1 and reach his eighth quarter-final in Rome in as many years.
No.2 seed opened his Internazionali BNL d’Italia campaign with a 6-3, 7-5 win over Radek Stepanek on Tuesday to reach the third round.
Novak will be back on the court after he’s been sidelined for three weeks due to wrist injury. He will play against Stepanek in R2.
World no.2 has been forced to withdraw from the Mutua Madrid Open, having suffered a recurrence of the right arm injury that afflicted him three weeks ago in Monte-Carlo.
Nole continues his clay court season at the second ATP World Tour Masters 1000 tournament on clay in 2014, the Mutua Madrid Open.
No.4 seed Roger Federer ended Novak’s reign in Monte Carlo with a 7-5, 6-2 win.
Nole defeated Spaniard Guillermo Garcia-Lopez 4-6, 6-3, 6-1 to reach his sixth Monte-Carlo Rolex Masters semi-finals.