Second-seeded Medina Garrigues, the champion in 2001, 2004, 2005 and 2006, fell to No. 7-seeded Mariya Koryttseva of Ukraine 6-2, 6-2.
Koryttseva will play in her first final of the year, and second of her career, against fifth-seeded Sara Errani, who downed Italian compatriot Pennetta 7-5, 6-3.
Pennetta had won their only previous matchup last year, but Errani has improved 150 spots in the rankings since then to No. 60.
Koryttseva and Errani will be playing for their first WTA title on Sunday. They are 1-1 against each other.
Medina Garrigues advances to semifinals in Palermo
Palermo reject Gunners link
Top-seeded Garrigues marches into SAR semifinals
Liverani joins Palermo
