Mueller was born and raised in upstate New York. Her father, Allen Mueller, worked as a Miami and Key West police officer, a high school teacher, a real-estate broker, and a part-time minister. He died in a motorcycle accident when Brooke was twelve. When Brooke was 14, her mother married Florida-based millionaire Kenneth Wolofsky and moved to Florida. Mueller was a cheerleader at the Benjamin School in Palm Beach, Florida. Mueller has a brother, Scott Allen Mueller, and a half-sister Sydney Wolofsky. Mueller's mother Moira Mueller Wolofsky Fiore is currently married to New York lounge singer Jon Fiore.
On May 30, 2008, Mueller married actor Charlie Sheen. Mueller gave birth to their twin sons, Bob and Max, on March 14, 2009. On December 25, 2009, Sheen was arrested at their rented house in the ski resort of Aspen, Colorado for attacking Mueller. He was later released from jail after posting an $8,500 bond. Sheen was charged with felony menacing, as well as third-degree assault and criminal mischief. On August 2, 2010, Sheen pleaded guilty to misdemeanor assault as part of a plea bargain that included dismissal of the other charges against him. Sheen was sentenced to 30 days in a drug rehab center, 30 days of probation, and 36 hours of anger management.
Sheen filed for divorce from Mueller in November 2010. On March 1, 2011, police removed Bob and Max from Sheen's home. According to People, social services took the children after Mueller obtained a restraining order against Sheen. The document said, "I am very concerned that [Sheen] is currently insane." The divorce was approved by a Los Angeles Superior Court judge and became effective on May 2, 2011.
In July 2011, Mueller completed a 45-day outpatient rehab program for alcohol and drug problems. She chose an outpatient program to have access to her children. "Brooke has decided to remove herself from the media spotlight, [so] she can focus on her recovery without distraction. Brooke's goal is to maintain her sobriety, and she believes this is the best option to reach that goal," her representative said in a statement. She reportedly checked back into rehab in December 2012.