Starmer held the first meeting of his top team with Britain's first woman finance minister Rachel Reeves and new foreign minister David Lammy in attendance.
The Labour leader told his ministers it had been "the honour and the privilege of my life" to be invited by King Charles III to form the government.
"We have a huge a amount of work to do, so now we get on with our work," he said.
Starmer spent his first hours in Downing Street on Friday appointing his ministerial team, hours after securing his centre-left party's return to power with a whopping 174-seat majority in the UK parliament.
Notable lower-ranking appointments included Patrick Vallance, chief scientific government adviser during the Covid-19 pandemic, who has been made a science minister.
James Timpson, whose shoe repair company employs ex-offenders, was also made a prisons minister.
Both would be given seats in the upper house of parliament in order to join the government as neither is an elected lawmaker.
Flag-waving crowds of cheering Labour activists on Friday welcomed Starmer to Downing Street.
"The work of change begins immediately. But have no doubt, we will rebuild Britain," Starmer said then.
Reiterating his five key "missions" for government in his maiden speech, the 61-year-old vowed to put the state-run National Health Service "back on its feet", ensure "secure borders" and provide safer streets.
But daunting challenges await his government, including a stagnating economy, creaking public services and households suffering from a years-long cost-of-living crisis.
"Changing a country is not like flicking a switch. The world is now a more volatile place. This will take a while," Starmer said.
- 'Historic' result -
World leaders lined up to congratulate the new British premier.
Starmer spoke by telephone with US President Joe Biden and "discussed their shared commitment to the special relationship between the UK and US and their aligned ambitions for greater economic growth", according to London.
He also spoke to President of the European Commission Ursula von der Leyen and Ukraine President Volodymyr Zelensky.
However, former -- and potentially future -- US president Donald Trump ignored Starmer, instead hailing the electoral breakthrough of his ally Nigel Farage's far-right Reform UK party.
Its capture of five seats and around 14 percent of the vote, alongside Farage becoming an MP on his eighth attempt, was one of the stories of the election.
But it paled in comparison to Labour's triumphs, after the party neared its record of 418 seats under ex-leader Tony Blair in 1997 by winning 412.
The Conservatives suffered their worst-ever defeat, capturing just 121 constituencies, prompting Rishi Sunak to apologise to the nation and confirm that he will resign as Tory leader once a successor is selected.
Former leader William Hague, a Sunak mentor who represented the same northern English constituency until 2015, conceded it was "a catastrophic result in historic terms".
A record 12 senior ex-government ministers lost their seats, alongside former prime minister Liz Truss, whose economically calamitous short-lived tenure in 2022 wounded the party irreparably ahead of the election.
It is now poised for another period of infighting between a moderate wing eager for a centrist leader and those who may even be willing to court Farage as a new leader.
- 'Challenges' -
The election also saw the centrist Liberal Democrats make their biggest gains in around a century, claiming more than 70 seats to become the third largest party in parliament.
But it was a dismal contest for the pro-independence Scottish National Party, which was virtually obliterated in Scotland. It dropped from 48 seats to just nine, with one still to declare early on Saturday.
The Green Party had its best general election, quadrupling its MPs count to four.
Meanwhile, an unprecedented six independent lawmakers were elected -- four of them defeating Labour candidates in districts with large Muslim populations and campaigns centred around the Israel-Hamas conflict.
Delight within Labour at its seats landslide will be restrained by recognition that it only secured around 34 percent of the vote -- the lowest ever to secure a majority.
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