Montolivo made his debut for the Italian national team in 2007 against South Africa, Since then, he represented the country in two FIFA Confederations Cups (2009 and 2013, winning a bronze medal in the latter edition of the tournament), as well as in the 2010 FIFA World Cup and UEFA Euro 2012, the latter where he played as a starter in the final. He also participated in the 2008 Summer Olympics. In total, he obtained 66 senior caps for Italy between 2007 and 2017, scoring 2 goals.