Bertinelli, who is best-known for her roles on the TV shows "One Day at a Time" and "Touched by an Angel," will help develop segments that reflect her personality and interests as a mother and working woman, said CBS Television Distribution.
For her first segment, Bertinelli traveled to New Orleans for a girls' guide to the gridiron at a "Monday Night Football" game.
Bertinelli also drops by the studio to show off her cooking skills, whipping up her special Louisiana gumbo.
The segment is set to air Tuesday.
"Valerie is the girlfriend and neighbor you wish you had. She lives her life with the same passion that our viewers do," host Rachael Ray said in a statement. "It is really exciting for me to have her as our 'correspondent extraordinaire.'"
"Rachael Ray" Executive Producer Janet Annino said: "Our viewers relate to Valerie's life, from raising a child, to divorce, to weight issues. We're going to let Valerie be Valerie."