The Australian put an end to Slovenian qualifier Polona Hercog's impressive run with a 6-3, 6-4 win in the third round of the clay court tournament.
The victory ensures Stosur will face off against Italian veteran Schiavone, who showed her mettle as she came back from a set down to beat Daniela Hantuchova 3-6, 6-2, 7-5 in a two-and-a-half hour marathon.
Stosur lost to Schiavone in last year's Roland Garros decider before scoring a consolation victory over the Italian at the season-ending championships in Doha.
Rome will be Stosur's last tournament before the French Open gets underway on Sunday week.
Stosur is the last Australian left in the draw in Rome after Jarmila Gajdosova was soundly thrashed by Chinese fourth seed Li Na, 6-1 6-2.
She next plays Hungarian Arn, who overcame Russian Elena Vesnina 3-6, 7-6, 7-6.
Tp seed Caroline Wozniacki advanced to the last eight by dispatching Belgian Yanina Wickmayer 6-1, 7-6.
The Dane now faces fifth-seed and twice runner-up Jelena Jankovic, who won through against Spain's Anabel Medina Garrigues 6-4, 2-6, 6-2.
Russia's Sharapova was again in ominous form in beating Shahar Peer 6-2, 6-2.
-AAP/ABCTags: sport, tennis, italy First posted May 12, 2011 22:21:00