While working as a showgirl at FeFe's Monte Carlo, a nightclub in New York City, Woodward met William Woodward Sr., a wealthy banker from a prominent old money family who served as Chairman of the Central Hanover Bank & Trust. It is speculated that she was Woodward's mistress. She was later courted by Woodward's son, William Woodward Jr., and married him in 1943 at St Luke's Memorial Episcopal Church in Tacoma, Washington. The marriage was a controversial one, and she was initially shunned by New York high society. Her mother-in-law, Elizabeth Odgen Cryder Woodward, objected to the marriage. She was eventually welcomed into prominent social circles and became a leading figure in society. She had two sons with her husband, William Woodward III and James Woodward. The Woodwards' marriage was an unhappy one, both having strings of affairs. Her husband asked for a divorce in 1947, but Woodward refused. In late 1955, there were a string of burglaries in the Woodwards' neighborhood in Oyster Bay. On October 30, 1955 Woodward and her husband returned to their country estate after attending a party hosted by Florence Tucker Baker in honor of the Duke and Duchess of Windsor, sleeping in separate bedrooms. Later that night Ann fired a shotgun twice, killing her husband. She claimed she had mistaken him for a burglar. She was not indicted for the shooting, and a Nassau County grand jury deemed the event an accident. The shooting led to Woodward becoming a cause célèbre in New York, and was referred to by Life as "The Shooting of the Century". Although never proven guilty of murder, she was shunned by high society for the rest of her life. She and her children moved in with her mother-in-law.