Replacing Beverley Hughes after her shock decision to stand down on Tuesday, Primarolo was picked for the job following nearly two years as health minister.
The Bristol MP was appointed financial secretary to the Treasury when the Labour Party came to power in 1997.
In 1999, Primarolo became Paymaster General overseeing the administration of the tax credit system.
Despite speculation that Children's Secretary Ed Balls was to replace Alistair Darling as Chancellor, both remained in position following the cabinet reshuffle on Friday.
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