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Katherine Cornell, a well-known stage star, played the role of "Sidney" in the 1921 Broadway production of Dane's play. Modern sources state that Clemence Dane's play, reportedly inspired by Henrik Ibsen's play Ghosts, was a favorite of producer David O. Selznick. Although most reviews and the copyright cutting continuity spell Katharine Hepburn's character name as "Sydney," the onscreen end credits give the name as "Sidney." According to advertisements, A Bill of Divorcement was "selected and presented under the auspices of Mrs. William Randolph Hearst for the benefit of the Free Milk Fund for Babies, Inc." Admission to the benefit screening, which occurred in New York on September 30, 1932, was $10.00 per ticket. The Hollywood premiere was a benefit for the Motion Picture Relief Fund, according to Hollywood Reporter. In an inter-office memorandum to various RKO executives, Selznick wrote that A Bill of Divorcement was "one of the best pictures, and possibly the most adult and intelligent picture, ever made." He then admonished his executives that "even if it is correct that the picture is 'too good for our audiences' (and I, personally, don't think there is such a thing), I do not think we should arrive at this conclusion in advance of its presentation to the public."
RKO borrowed David Manners from Warner Bros. for the production. According to a Film Daily news item, Reginald Owen was assigned to play a "straight, romantic role" in the film, but his participation in the final film has not been confirmed. Billie Burke, a veteran stage and silent screen star, made her sound feature film debut in this film. Burke's husband, Florenz Ziegfeld, died during the production. According to RKO records, Burke was paid $1,500 per week for a total of four weeks, while John Barrymore's contract guaranteed him $50,000 and 15% of the film's gross after the first $1,000,000 in profits.
Hepburn (1907-2003) made her screen debut in the film. The Variety reviewer astutely noted that Hepburn "has a vital something that sets her apart from the picture galaxy" and speculated that if she repeated her performance in a similar role in her next picture, she would be "headed for the cinema heights." (In her next film, Christopher Strong, Hepburn played a strong-willed aviatrix. Although the actress again enjoyed critical acclaim, the film did not do well at the box office. Nevertheless, her performance in A Bill of Divorcement earned her star status at RKO.) Several reviewers compared Hepburn to Greta Garbo, stating that while Hepburn lacked Garbo's mystery, she possessed the same striking, powerful presence as the Swedish star. A contemporary article in New York Times gives the following account of Hepburn's casting: Her performance as the "Amazon Queen" in the 1931 Broadway play The Warrior's Husband landed her a screen test with RKO. After executives saw the finished film in the projection room, they signed Hepburn to a contract, which called for her to appear in two films per year, with time off for stage plays. Hepburn was paid $1,500 per week for a total of $7,125. (Modern sources note that a few scenes with Hepburn had to be re-shot after the initial four weeks of production.) Prior to Hepburn's involvement, Irene Dunne and Anita Louise were considered for the role of "Sidney," according to a June 1932 Film Daily news item. Modern sources add that Jill Esmond also was offered the role, but turned it down. Modern sources note that the film's proposed budget of $300,000 prohibited the hiring of Irene Dunne, a prominent RKO star who was earning $15,000 per film at the time.
Modern sources add the following information about Hepburn and the production of this movie: For her screen test, Hepburn chose, not a scene from A Bill of Divorcement, but a scene from the Philip Barry stage play Holiday. The test, directed by RKO talent scout Lillie Messenger, was shot in New York, with Alan Campbell playing opposite Hepburn. Although RKO executives in Los Angeles were less than impressed by the footage, director George Cukor was struck by the way that Hepburn had placed a glass on the floor of the set and voted to cast her. Backed by Selznick, who also felt that Hepburn had a striking, fresh screen presence, Cukor brought Hepburn to Los Angeles. Before shooting began, Cukor arranged for Hepburn's hair to be re-styled and her facial freckles covered with makeup. In preparation for her first film role, Hepburn spent time on the RKO lot, studying each aspect of the filmmaking process. In modern interviews, Hepburn praises Barrymore for teaching her a "tremendous lot" about film acting during this production.
Modern sources add the following crew credits: W. Franke Harling (Piano concerto composer); Josette De Lima (Costumer) and Mel Berns (Makeup artist). Modern sources credit Dennis O'Keefe (then known as Bud Flanagan) as a "Dance extra." A British version of Dane's play, titled A Bill for Divorcement, was filmed in 1922. Denison Clift directed Constance Binney and Fay Compton in that silent version. RKO made a second version of Dane's story in 1940 (see below).