The Prime Minister, who has promised to restore hope to the nation after a landslide election victory, also named Angela Rayner as his deputy and appointed Yvette Cooper as Home Secretary.
David Lammy has been given the Foreign Secretary role, putting to bed some speculation over whether he would get the post he shadowed in opposition.
The first batch of appointments contained no surprises. Pat McFadden, who played a central role in shaping Labour's election campaign, was named Chancellor of the Duchy of Lancaster.
John Healey is Defence Secretary, Shabana Mahmood is Justice Secretary, Wes Streeting is Health Secretary, Bridget Phillipson is Education Secretary and one-time leader Ed Miliband is Energy Secretary.
Ms Reeves, a self-confessed "geek" and schoolgirl chess champion, is one of Sir Keir's closest allies and will be the first woman to lead the Treasury in its 1,000year history.
She said it was "a huge privilege" to be the first female Chancellor.
Inequality
She added: "So every young woman and girl watching - let today show that there should be no ceilings on your ambitions, your hopes or your dreams.
But there is a deeper responsibility too to women whose work is too often undervalued, who have borne the brunt of inequality."
She said "there is no time to waste" as she addressed Treasury staff for the first time. Ms Reeves who posed outside her official residence at 11 Downing Street, added: "I have been a Member of Parliament for 14 years now.
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