Despite a number of chances to hit the back of the net, Cesare Prandelli's side ended up succumbing to three second half strikes that were aided by some dismal defending.
There was a glut of chances throughout the game and it was remarkable that the score was level at the break. However, the second half saw Dick Advocaat's side find the finishing touch with Alexander Kerzhakov and a double from Roman Shirokov exploiting some glaring defensive mishaps in the Italian defense in their only warmup match before the tournament in Poland and Ukraine.
The game began very evenly with both sides looking to attack and seize the initiative. Daniele De Rossi volleyed wide of the post after three minutes, and seconds later Alan Dzagoev saw his drilled effort saved by Gianluigi Buffon.
The Azzurri continued to push forward, and when Andrea Pirlo spotted Mario Balotelli's diagonal run across the top of the box in the seventh minute he guided a trademark exquisite pass on to the striker's chest. Balotelli then lashed a volley at goal but it was straight at Vyacheslav Malafeev, who deflected the ball behind.
Russia was unperturbed, and before 10 minutes had been played they hit the woodwork through Kerzhakov. Andrei Arshavin passed in to Shirokov who, with his back to goal, dinked the ball over the defense and into the path of the striker, and he rattled the near post with his attempt.
The game soon settled down after the high-tempo start but sparked back to life after a 10-minute subsidence in the action. De Rossi and Shirokov both went close and in the 26th minute Pirlo picked out the Roma midfielder with another beautiful pass. De Rossi squared the ball across the box but it was agonizingly out of reach of Balotelli, who was unable to turn in to an open net.
The opportunities kept flowing and Russia had three more chances to find the net. Konstantin Zyryanov blazed over from inside the area and moments later saw another effort scrape the outside of the post. Then, in the 32nd minute, Yury Zhirkov burst in at the back post and slammed an effort towards the near post, but Buffon had it covered with the help of his post.
With the second half continuing in a similar vein, Cassano volleyed over from Balotelli's superb pass, and in the 52nd minute Claudio Marchisio completely mishit the ball after being put through on goal and Igor Akinfeev was able to make an easy save.
Despite Italy's impressive start to the half, it was Russia who finally got the ball in the net on the hour mark. Some excellent play by Dzagoev and Shirokov on the right ended with Kerzhakov arrowing a perfectly-executed volley into the bottom corner after the ball looped up from his first touch.
Italy tried to find the equalizer but they were struggling to test Akinfeev in the Russia goal. With 15 minutes remaining Dick Advocaat's side doubled their lead after a mix up between Cristian Maggio and Morgan De Sanctis saw Arshavin steel in and get a foot on the keeper's clearance. The ball fell to Shirokov, who will never have an easier goal as he rolled the ball into a vacant net.
The Azzurri were crestfallen, and the scoreline got even worse in the dying moments. Aleksandr Kokorin's shot looked to be going wide but a touch from Maggio saw the ball loop up and Shirokov pounced to nod the ball into the net.
Cesare Prandelli may well be ruing the cancelled friendly against Luxembourg as he has no other chance to try other options ahead of Euro 2012. Russia, however, will take huge confidence from the result and now the tournament will not come soon enough, with the opener against Czech Republic just eight days away.