The Charmed star, who wed David Donoho in 2004, is citing irreconcilable differences, according to TMZ.com.
The couple has three children together - Finley, seven, Riley, five, and two-year-old Kelley. Combs is expected to seek joint custody of the kids.
She was previously married to actor Bryan Travis Smith. That union ended in 2007 after four years.
Actress Holly Marie Combs is a mom again after giving birth to her second child on Thursday.
The Charmed star and her husband, David Donoho, welcomed baby Riley into the world in Los Angeles' Cedars-Sinai Medical Center.
According to People, little Riley weighed in at 8.5 pounds.
Proud dad Donoho tells the magazine, "Everybody's great. Holly is tired, but she's fine. Riley came right out and, as soon as he heard Holly's voice, he smiled."
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Married Feb. 14, 2004 at the San Ysidro Ranch in Santa Barbara; combs was seven months pregnant at the time; Combs filed for divorce in November 2011, citing irreconcilable differences as the reason for the split