Grylls will work alongside the UK Scout movement's first chief commissioner, Wayne Bulpitt, whose appointment was also announced today.
A mountaineer and former soldier, Grylls presents the TV series Born Survivor in which he undertakes exploits such as wrestling alligators and eating porcupine.
He is the tenth and youngest Chief Scout, replacing Peter Duncan, the former Blue Peter presenter, who has held the role since 2004.
Grylls will be supported in the role by Bulpitt, who as the UK Scouts' first chief commissioner will be responsible for managing the movement's adult volunteer leaders.
Bulpitt, from Guernsey, has been involved in the Scout movement since he was a boy and has been a managing trustee of Scouting in Guernsey.
Grylls said: "I have always loved helping young people live their dreams and to taste real adventure, as well as getting caked in mud! I also hope I can use this post to encourage masses of adults in the UK to volunteer as leaders. The young people in this country need them like never before."
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