DeVos is the second woman Trump has tapped to fill a cabinet position. He earlier named South Carolina Governor Nikki Haley to be US ambassador to the United Nations.
DeVos is a Republican megadonor from Michigan who has been active in promoting school choice, a movement that advocates the use of tax credits and vouchers to allow parents to opt out of the public school system.
"Under her leadership we will reform the US education system and break the bureaucracy that is holding our children back so that we can deliver world-class education and school choice to all families," Trump said.
She is the sister of Erik Prince, the founder of Blackwater USA, a security firm whose operations in Iraq aroused controversy. Her father was the founder of an automobile parts supplier.
Her husband's father Richard DeVos was ranked Number 88 on Forbes' list of US billionaires, with a fortune estimated to be worth USD 5.4 billion.
"The status quo in education is not acceptable," DeVos said in a statement accepting the offer of the education secretary position.
"Together, we can work to make transformational change that ensures every student in America has the opportunity to fulfill his or her highest potential.
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