The Prime Minister also appointed David Lammy as UK foreign secretary, John Healey as defence secretary in UK, and Yvette Cooper as home secretary in his cabinet.
The newly elected Prime Minister of the United Kingdom, Keir Starmer has appointed Angela Rayner as his deputy.
Starmer, who made this appointment shortly after his assumption of office on Friday, also announced Rachel Reeves as the first female chancellor in Britain.
The Prime Minister also appointed David Lammy as UK foreign secretary, John Healey as defence secretary in UK, and Yvette Cooper as home secretary in his cabinet.
Rachel Reeves, the 45-year-old, is a self-confessed "geek" and schoolgirl chess champion.
She is one of Sir Keir's closest allies and will be the first woman to lead the Treasury in its 1,000-year history.
Angela Rayner had earlier been the first arrival in Downing Street this afternoon as Labour's deputy leader walked down the famous London street before being named Deputy Prime Minister.
She was also appointed Levelling Up, Housing and Communities Secretary as she was handed a portfolio focused on her party's planned house building blitz.
Ms Rayner was later followed into Downing Street by David Lammy, Yvette Cooper, John Healey, and Wes Streeting as Sir Keir looked to fill key roles in the Foreign Office, Home Office, Ministry of Defence and Department of Health and Social Care.
He began his Cabinet appointments after earlier stepping through the entrance to No10 as the new Labour premier with a vow to 'immediately' begin work to 'rebuild Britain'.
The Labour leader was applauded by staff inside the famous black door as he walked inside with wife Victoria after making his first address to the nation as the new premier.
The 61-year-old acknowledged 'weariness at the heart of the nation' after his so-called 'loveless landslide' in the general election.