Gentiloni, 62, was asked by President Sergio Mattarella yesterday to form a new centre-left government that will guide Italy to elections due by February 2018, following the resignation of outgoing Prime Minister Matteo Renzi.
Gentiloni tapped Angelino Alfano -- a former protege of ex-prime minister Silvio Berlusconi -- to take over his role as foreign minister.
Pier Carlo Padoan stays on as finance minister in a move likely to reassure the markets that the eurozone's third largest economy can deal with a budding crisis in the banking sector.
The swearing-in ceremony was set to take place later today.
"Good luck to Paolo Gentiloni and the government with the job. Long live Italy," Renzi said on Twitter.
Opposition parties have slammed the softly-spoken Gentiloni as little more than a Renzi puppet.
The founder of the anti-establishment Five Star movement, comic Beppe Grillo, said appointing a Renzi ally as premier ignored the wishes of those who voted against the outgoing PM's referendum.
Grillo said the party would organise a mass protest for January. But Milan's FTSE Mib saluted the new prime minister, remaining positive throughout the day.
Silver-haired Gentiloni, a one-time student radical from an aristocratic family, will seek parliamentary approval of his new government on Tuesday or Wednesday.
Among the most pressing issues facing the new government is the fate of the troubled BMPS.
The institution, the third largest in Italy, had requested extra time from Europe to plug a gaping hole in its finances, but reports on Friday that the European Central Bank had refused spooked the markets.
Oanda analyst Craig Erlam said investors were "more optimistic" the bank could raise the 5 billion euros (USD 5.29 billion) needed to avoid a handout and were relieved political uncertainty had been removed in the short term at least.
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