"I didn't want to be the Education Secretary who didn't know how to spell potato," Spellings joked, describing how she read books and sought advice from a former show contender and her daughters.
In the end, Spellings said she thinks the effort was worth it. She came in second behind the actor Michael McKean, best known for his role as 'Lenny' on the television show "Laverne and Shirley" and for the movie "This Is Spinal Tap."
Placing third was actor Hill Harper, from the television show "CSI: NY."
"I think I held my own," Spellings said in an interview Tuesday, hours before the show aired. She noted McKean had an edge, having been on the show before.
Spellings was the first Cabinet secretary ever to appear on the popular quiz show. She said she'd like to return for another try.
She said she didn't realize how much skill went into hitting the buzzer at just the right moment after host Alex Trebek read a clue. She said she often hit it too early and as a result didn't get picked to tackle a category.
Spellings' strong subjects included international language and business.
She was asked to appear after the show's producer read a magazine article in which Spellings said she was a "Jeopardy!" fan.
Each celebrity earns at least $25,000 for the charity of his or her choice, and the winner gets $50,000 for a charity.
Spellings' winnings from the show, taped in New York last month, went to ProLiteracy Worldwide - an international literacy organization.
Trebek said "Jeopardy!" picked the charity for Spellings to comply with government ethics rules.