Hours after speaking to French President Emmanuel Macron about the numbers of migrants travelling from Libya to Italy, Mr Gentiloni spoke to EU chief Jean-Claude Juncker.
According to government sources the pair also discussed proposals to reform the bloc’s labour rules, which have sparked tensions between European leaders.
Under current legislation, firms are able to send temporary workers from low-wage countries to richer nations without having to pay their local social charges.
But Mr Macron is among those demanding that changes are made and is using fears about the possible collapse of the Brussels bloc to scare EU members into backing his proposals.
His proposal, which is backed by Germany and Austria, would limit the job duration of the detached employees to 12 months – half of the period proposed by the EU’s executive Commission.
The row is driving a wedge between the richer EU nations and their poorer neighbours, where most of the cheap labour comes from.
It is likely Mr Juncker’s call was to gauge where the Italian PM stands on proposals to change current rules, given Mr Macron has faced strong criticism from Poland and Hungary over his plans to reduce the effect of ‘social dumping’ on the host nations’ economies.
Italy also wants to replicate a deal with Libya that the EU struck with Turkey last year, largely shutting down the migrant route through the Balkans.
With a national election looming next year, the government in Rome is under pressure to show it can slow down migration.
The phone call comes ahead of a summit in Paris on Tuesday, which will be attended by German Chancellor Angela Merkel, French President Emmanuel Macron, Spanish Prime Minister Mariano Rajoy and European Commission Vice President Federica Mogherini.
Migration is expected to be high on the agenda for Tuesday’s meeting, with both Mr Gentiloni and Mrs Merkel facing general elections in the coming months.
Official figures show arrivals in Italy from North Africa dropped by more than 50 per cent in July from a year earlier.
August arrivals so far are down even further, according to the International Organisation for Migration (IOM).
July and August were expected to be peak months for migrant boats because of favourable sea conditions.
The EU’s border control agency Frontex believes changeable weather and the increased Libyan coastguard presence contributed to July’s decline.
After next week’s meeting, Mr Gentiloni and Mr Macron will then have a bilateral meeting in Lyon on September 27.
Additional reporting by Maria Ortega