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On being nominated to the post in November, she was called "a brilliant and passionate education advocate" by Mr Trump.
But her performance before a nomination committee last month made the news for all the wrong reasons and she now faces the chance of not landing the job.
It is already as good as certain that Democrats will not vote for Mrs DeVos when they make the decision in the Senate on Tuesday. But two Republican senators have also said they will not back her, leaving the vote tied at 50-50.
If it stays that way, Vice-President Mike Pence would cast the deciding vote - but one more Republican defector would mean Mrs DeVos not getting nominated (last week, the New York Times even went as far as appealing to "one Republican with dignity" to vote against her).
Labour unions, rights groups and teaching organisations have also spoken out against her nomination.
So just why has she proven so unpopular?
Mrs DeVos, 59, is a wealthy Republican Party donor and a former Michigan Republican Party chairwoman who has long campaigned for education reform in the state.
Her husband Dick DeVos was a CEO of the beauty and nutrition giant Amway and her brother is Erik Prince, the founder of the controversial private security company Blackwater.
It is not clear how much the DeVos family support Mr Trump or his agenda - in 2015, they gave money towards the campaigns of Jeb Bush and Wisconsin governor Scott Walker. And, in an interview last March, she described Mr Trump as "an interloper" who did not represent the Republican Party.