A publicist for Houston confirmed to The Associated Press that the Grammy-winning, superstar singer had filed for divorce after 14 years of marriage.
Publicist Nancy Seltzer declined to reveal where or when Houston filed the divorce papers, and said the singer had no statement to make.
"I can just confirm that she has filed for divorce," Seltzer said Wednesday.
Brown's lawyer said Houston had filed papers for a legal separation.
Houston and Brown, who had a home in Alpharetta, Ga., have one child, a 13-year-old daughter, Bobbi Kristina.
When they wed in 1992 the union seemed to outsiders to be a mismatch. Houston - once one of the best-selling singers in history - was a glamorous, pop superstar with a super-clean, princess-like persona, whereas Brown, who rose to fame as a member of the boy band New Edition before striking out on his own, was a sometimes coarse R&B singer with a more street-wise image.
But as the years wore on, it would become hard to determine which one was more troubled. Brown - best known for hits like "My Prerogative" and "Every Little Step" - would be arrested numerous times for drugs and alcohol, while Houston's own battles with substance abuse sullied her image.
Together, the two were a tabloid editor's dream. When Brown was released from a stretch in jail a few years ago, an ecstatic Houston greeted him by jumping into his arms and throwing her arms and legs around him before a throng of fans and media.
And in a 2002 ABC interview with Diane Sawyer, an erratic-sounding and wan-looking Houston, with a profusely sweating Brown by her side, admitted dabbling in drugs but denied using crack, then uttered the now famous phrase: "Crack is wack."
Houston checked into a drug rehabilitation program in 2004 and again in 2005, announcing the second time that she was also using prayer to help overcome her drug problems.
Brown said at the time he was doing what he could to help her.
"It takes two to make things work, so I have to be there for her just like she was there for me when I went through my rehab stint," he told "Access Hollywood".
The couple did separate for a time a few years ago, but their marriage endured, despite rumors and speculation. Their life was put on display last year with Brown's reality series, "Being Bobby Brown" on Bravo. The show actually made Brown look like a stable influence, while a jittery Houston was on display; the couple often crudely talked about their marriage and love life.
But earlier this year, the speculation of a possible split intensified. Brown's sister made headlines when she alleged in a National Enquirer interview that Houston was addicted to crack. She also supplied photos of what she said was Houston's bathroom, littered with garbage and evidence of drug use.
Phaedra Parks, an entertainment lawyer in Atlanta who represents Brown, said he told her Wednesday that Houston recently filed paperwork in California seeking a separation.
"It is a legal separation. It is not a divorce or a divorce petition," Parks said.
Parks said she has not seen the documents and didn't know which court they were filed in.
Asked about speaking with Brown, Parks said, "Bobby's not speaking with anyone at this time."
Recently, Houston has made attempts to clean up her public image. On Tuesday night, she attended a public event with cousin Dionne Warwick and mogul and mentor Clive Davis in Beverly Hills. And she is working on an album of new material; she hasn't released a record since 2002.
Houston, 43, won multiple Grammys in the 1980s and 1990s, including two for the megahit "I Will Always Love You," from the 1992 film "The Bodyguard," in which she also starred opposite Kevin Costner.
"I Will Always Love You," won Grammys for record of the year and best female pop vocal, and "The Bodyguard" soundtrack won album of the year.
Houston also won Grammys in 1985 and 1987 for best female pop vocal for "Saving All my Love for You" and "I Want to Dance With Somebody (Who Loves Me)." She won a Grammy for best female R&B vocal in 1999 for "It's Not Right But It's Okay."
Her musician husband recently reunited with New Edition for a show at July's Essence Musical Festival. The show got mixed reviews from the audience when Brown jumped suggestively around the stage and made vulgar remarks about his sex life with Houston.
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