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.
Opposition parties slammed the softly-spoken former foreign minister as little more than a Renzi puppet, but Milan's FTSE Mib saluted the move, up 1.22 per cent at 1030 GMT.
Silver-haired Gentiloni, a one-time student radical from an aristocratic family, is expected to keep the cabinet largely untouched and present his final list to the president by the close of play today.
The biggest cabinet seat to fill is the one left vacant by Gentiloni himself, that of foreign minister.
Political watchers say it could go to Piero Fassino, a member of Renzi's centre-left Democratic Party (PD) who has previously held the justice and foreign commerce portfolios.
Interior Minister Angelino Alfano, who was Renzi's deputy and heads the New Centre-Right (NCD) party, is also tipped for the post.
Should it go to Alfano, the interior portfolio could be handed to Domenico Minniti, the state secretary with responsibility for the security services under Renzi.
Pier Carlo Padoan is expected to stay on as finance minister to reassure Europe that the eurozone's third-largest economy is on solid ground.
Among the most pressing issues facing the new government is the fate of Italy's Monte dei Paschi di Siena (BMPS) bank.
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.
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