No mountain range separates Italy and Greece. The Adriatic Sea (specifically its southern portion, the Ionian Sea) forms the natural boundary between the two countries.
At their closest point—between Italy's "heel" (Salento peninsula) and Greece's western coast (Corfu and the mainland near Igoumenitsa)—the distance is approximately 45 nautical miles (83 km). Ferries connect Brindisi, Bari, and Otranto (Italy) with Igoumenitsa, Patras, and Corfu (Greece) in 8-16 hours.
The confusion may stem from the Dinaric Alps, which run along the eastern Adriatic coast through Slovenia, Croatia, Bosnia, Montenegro, and Albania—but these mountains lie entirely east of the Adriatic, not between Italy and Greece.
Geologically, both countries share the Alpine-Himalayan orogenic belt, but the Adriatic plate's subduction created the sea barrier that defines their modern border.