Napolitano appeared to shrug off the petition, however, telling reporters that the petition should follow due process and would "run its course."
M5S' move on Thursday drew widespread criticism from fellow politicians. Prime Minister Letta said the bid was "an atrocious act aimed only a taking out the fundamental element of our democratic system," ANSA reported, while a member of the "New Center right" party – a splinter group from Berlusconi's party – said the move was "simply absurd."
Napolitano is widely seen as a stalwart of the Italian establishment that has helped steer the euro zone's third largest economy throughout the financial crisis.
In 2013, he reluctantly delayed his retirement due to the country's deep political crisis which threatened to further derail the economy following inconclusive elections in February last year.
Napolitano had tried to negotiate with the MS5 to form a coalition government with the center-left Democratic Party (PD) led by Enrico Letta, the current prime minister, but the movement had refused the offer on the grounds that it did not want to share power. M5S has since then been left out in the cold after a fractious alliance was formed instead between the PD and Silvio Berlusconi's center-right "Forza Italia" which itself ended acrimoniously late last year.
The bid to impeach Napolitano comes after months of criticism from M5S – a populist anti-Europe, anti-austerity party that calls for a new political order in Italy –which sees the president as responsible for maintaining the status quo of the Italian establishment.
(Read more: Italy braces for comedian's 'unstoppable epidemic')
Defenders of Napolitano argue that he saved Italy from the ongoing political deadlock in the aftermath of inconclusive elections and has since then tried to maintain political stability in order to salvage the economy. Italy has one of the highest public debt piles in the euro zone -- second only to Greece -- of 2.1 trillion euros ($2.84 trillion) equating to a debt to GDP ratio of 130 percent.
Political instability within the fractious coalition government of Silvio Berlusconi's "Forza Italia" party and its center-left partners, the Democratic Party (PD) led by Prime Minister Enrico Letta, caused much-needed economic reforms to take a back seat last year.
Anti-establishment movements like M5S have grown in popularity against a backdrop of increasing public dissatisfaction with Italian politics. In December, protests swept through Italian cities as frustrations over political stalemate, unemployment (the jobless rate in Italy jumped from 11.3 percent in November 2012 to 12.7 percent a year later, data from Eurostat shows) and austerity policies united large swathes of the populace against the government.
(Read more: Italy could be racked by violent unrest, president warns)
However, there are signs that Italy is picking up, economically at least.
Although the country has experienced a protracted downturn over the last two years, fourth quarter GDP data due in February is expected to show it finally exited recession at the end of 2013. The government is also planning to privatize state assets including chunks of the postal service and air traffic control agency in 2014, in order to bring down public debt.
(Read more: Italy makes last-minute 2014 budget dash)
The Bank of Italy estimates that GDP will grow by 0.7 percent in 2014 and by 1 percent in 2015.
- By CNBC's Holly Ellyatt, follow her on Twitter @HollyEllyatt.
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