Murray made it through to his first Rome final with a clinical 6-2 6-1 win over unseeded Frenchman Lucas Pouille while world number one Djokovic showed his staying power in a 2-6 6-4 7-6(5) victory over Japanese sixth seed Kei Nishikori.
"Any time you get the chance to play the best players, especially right before a slam, is great preparation," Murray, who has won just one of his past 13 matches against Djokovic, told reporters.
Serena Williams moved within sight of a fourth Italian Open triumph when she brushed aside Irina-Camelia Begu to set up an all-American showdown with young compatriot Madison Keys.
Williams, who looks in fine form for the defence of her French Open title which begins next weekend, overpowered her Romanian opponent 6-4 6-1.
The world number one will now be a hot favourite to land the 70th career title of her storied career on Sunday when she faces the 24th-ranked Keys, who defeated Spain's Garbine Muguruza 7-6(5) 6-4 in the other semi-final.
Williams has looked vulnerable this season, has not competed for two months and pulled out of last week's tournament in Madrid with flu yet she demonstrated she will still take some beating at Roland Garros.
There were brief interruptions for rain on a dank, wet day but after Begu, ranked 35, had extended Williams in the opening set, the 34-year-old dismissed her challenge mercilessly in the second.
Keys has been enjoying her best claycourt performance in Europe and caused a shock with her win over Wimbledon finalist Muguruza but beating Williams, who has won 15 successive matches against Americans, is a challenge of a different magnitude.
Earlier, Murray, who lost to Djokovic in the Madrid final last weekend, continued his fine form by keeping his concentration through two rain delays and taking just shy of an hour to dispose of qualifier Pouille.
The 22-year-old Frenchman has an exciting future but the gap with twice grand slam champion Murray was painfully evident.
The second seeded Scot has yet to drop a set this week.
"Clay is not my most natural surface but because of the wins I've had on it in the last few years ... I believe that I can compete with the best players on this surface now," he said.
(Writing by Ian Chadband and Pritha Sarkar in London; editing by Ken Ferris and Ian Ransom)
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