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France
Picture provided by Marco Materazzi's official Twitter page
Both for geographical and historical reasons, France really does represent the biggest rivalry Italians could ever feel. However, despite some relevant victories, such as the ones of 1986, 1998 and 2000, the French do not really have many arguments on their favor against Italy, statistically speaking.
As a matter of fact, out of the 37 games ever disputed, the Blues only managed to win nine times and to draw 10. Italy, instead, won the other 18, including the 2006 World Cup final.