Irina-Camelia Begu was the highest seed to fall during the first-round action at the XXVI Italiacom Open.
The Romanian sixth seed bid farewell to Palermo after one hour and 32 minutes of play produced a 7-5 6-2 win for Renata Voracova.
The 29-year-old Czech will face home wildcard Corinna Dentoni in the second round with Italian favourite and top seed Sara Errani waiting for Barbora Zahlavova-Strycova following the Plzen native's 6-4 6-4 victory over Kristyna Pliskova.
Pliskova's eighth-seeded twin sister Karolina will also go no further after slipping to a 7-5 7-5 defeat to Germany's Dinah Pfizenmaier, who will take on Anabel Medina Garrigues.
The Spaniard beat Kristina Barrois of Germany 6-4 4-6 6-2 while her seventh-seeded compatriot Silvia Soler-Espinosa can look forward to facing Mirjana Lucic-Baroni after the Croatian beat Mariana Duque Marino 6-3 6-3.
Czech fourth seed Klara Zakopalova dismissed former world number 10 Flavia Pennetta 6-2 2-6 6-3 to book a match against Bruneck-born Karin Knapp, who made light work of Brazil's Teliana Pereira on her way to a 6-3 6-2 win.
Elsewhere, Polona Hercog beat Eva Birnerova 6-4 6-1 to meet second seed Roberta Vinci after last year's US Open quarter-finalist beat fellow Italian Giulia Gatto-Monticone 7-6 (8/6) 6-3.