Cameron Dick is Deputy Premier, marking the first time since 2005 the Queensland Labor party has two men at the helm.
They were met with applause as they entered the caucus room in Brisbane on Friday morning.
When they emerged - both elected unanimously and unopposed to their roles - a new-look cabinet was revealed.
Nikki Boyd, Bart Mellish, Michael Healy, Lance McCallum and Charis Mullen will all be given frontbench positions.
Mark Bailey, Stirling Hinchliffe and Craig Crawford have lost their ministerial portfolios.
"They are younger, they are energetic, they are ready to deliver a fresh new approach for Queenslanders," Mr Miles said of his new cabinet members.
Outgoing premier Annastacia Palaszcuk did not attend the caucus meeting.
Mr Miles and Mr Dick were later sworn in at a Government House ceremony.
The new premier backed Labor to win next year's state election.
"While we are the underdog I am confident we can do this," he said.
Mr Miles is set to unveil his priorities at a 2pm AEST press conference.
The cost of living, housing, education and youth crime are expected to be high on the agenda with reports he will also announce new emission reduction targets.
"Ultimately, I'm a suburban Queensland dad with three kids, and so many Queenslanders are like me, and I want to demonstrate to them that I understand what concerns them in their day-to-day lives and how government can help them," Mr Miles said earlier on Friday.
He has already confirmed an independent authority will be established to review 2032 Brisbane Olympic infrastructure plans, with the controversial $2.7 billion Gabba rebuild on the list.
Mr Miles emerged as the frontrunner to take over the top job soon after Ms Palaszczuk's shock announcement on Sunday.
An emotional Ms Palaszczuk stepped down after almost nine years as premier, quickly endorsing Mr Miles as her successor.
However he faced opposition with Health Minister Shannon Fentiman announcing a leadership tilt.
Barely 12 hours later Ms Fentiman withdrew her bid, saying it was clear Mr Miles had the numbers to become premier amid speculation of a backroom union deal.
Annastacia Palaszczuk shocked colleagues when she announced she would resign as premier. (Jono Searle/AAP PHOTOS)
Big shoes await Mr Miles.
Ms Palaszczuk was Australia's longest-serving sitting premier, enjoying 12 years as party leader.
She went from an opposition with seven seats to becoming premier in 2015, going on to become the first woman to lead a party to three state election victories.
Ms Palaszczuk will also depart her Inala seat by year's end, prompting a by-election.
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