Holders Spain on Sunday arrived first at Kiev's Olympic Stadium to prepare to defend their European Championship title, television pictures showed.
La Roja, led by Xabi Alonso and Alvaro Arbeloa, made their way from the bus to be followed minutes later by the Azzurri, with captain Gianluigi Buffon leading his side and star striker Mario Balotelli coming out last.
Both teams then made their way out to inspect the pitch.
Italy midfielder Thiago Motta on Sunday nearly missed the bus taking the team to the final of Euro 2012, television pictures broadcast by UEFA showed.
The door to the Azzurri's bus was closed when the Brazil-born star ran out of the team hotel and was able to get on board just in time, as a dozen or so hotel staff who had turned out to wish them well looked on with grins on their faces.
Italy are hoping to prevent holders Spain from retaining their title in the match, which kicks off at 1845 GMT in the Ukrainian capital, Kiev.