The businesswoman has put her name to an "exclusive" deal with the rival station.
Her new show, which is due to air later this year, will see her help candidates land internships with companies.
Devey, 55, will appear in one more series of BBC2âs Dragonsâ Den but it is understood the BBC was unable to compete with the money offered by C4.
Candidates in her new series, which has a working title The Intern, will be thrown in at the deep end for a week to see if they have the abilities to cope with the pressures of their chosen profession.
Self-made millionaire Devey  who set up the Pall-Ex freight network  said: âI am thrilled and excited by the prospect of working with Channel 4.
"The formats for my new shows are fantastic and Iâm sure they will prove compulsive viewing.â
She has previously featured in C4âs Secret Millionaire.
Hilary joined Dragonsâ Den last year, replacing James Caan.
A spokeswoman for the BBC said: âHilary has been a formidable Dragon in the Den and weâre sorry to see her go.
âShe will be breathing fire throughout the new series of Dragonsâ Den coming up in the autumn on BBC Two.â
An insider said: âWe are always mindful of how much we spend, unfortunately the financial offer from Channel 4 made it impossible for us to compete and so the upcoming series will be her last.â
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