The 'Blow Me (One Last Kiss)' singer will begin appearing in print and TV campaigns for the cosmetics brand beginning this autumn, the company announced on Monday.
"Joining a group of women who have always inspired me - to laugh out loud, let my guard down, or play around with my beauty look - is such an honour," Pink said.
"I have a lot to celebrate. I called my new album The Truth About Love, and the truth is that I have my beautiful family and baby girl, my new music and now my partnership with CoverGirl to love."
CoverGirl vice president Esi Eggleston Bracey added: "Pink is a powerful and provocative role model, who has always been an advocate of individualism and making no apologies for who you are."
"We love the energy and confidence that she radiates, and the fact that inside and out she's as cool as she looks. She's an awesome addition to our CoverGirl family."
Pink joins stars such as Taylor Swift, Modern Family's Sofia Vergara, Drew Barrymore and Ellen DeGeneres as a spokeswoman for the company.