Written By: Ben Cosgrove

Sure, we all loved Lucy, but which one? The rubber-faced Lucy Ricardo of her classic TV sitcom, I Love Lucy? That goes without saying. But what about Lucille, the struggling but determined Hollywood starlet who spent two decades lingering in B-movie purgatory? Or the powerful Ms. Ball, the behind-the scenes TV pioneer and the medium’s first major female executive?

Truth is, Lucille Ball lived several fascinating lifetimes, many of them captured by LIFE’s photographers on her way up the showbiz ladder. She was the vice president of Desilu Productions, making her television’s first female mogul. The strain of running a business with her husband and longtime onscreen foil, Desi Arnaz, and Desi’s drinking ultimately doomed the partnership. The couple divorced in 1960, and Ball bought Arnaz out of the business in 1963. Lucy went on to star without Desi in hit sitcoms The Lucy Show (1962-68) and Here’s Lucy (1968-74). Desilu, meanwhile, remained a prolific producer of classic 1960s shows like The Untouchables, Mission: Impossible and Star Trek.

Here, LIFE.com presents photos none of which ever ran in LIFE of Lucille Ball, including at least one surprisingly sultry 1942 portrait (slide #1) by John Florea, made when Ball was known as “Queen of the B’s” for the string of sub-par films that had failed to make her a star. Years of dues-paying hard work are apparent in her eyes. And yet, there is something sweetly defiant, too, about her look: a sense that, with a little luck, her big break is just around the corner.

Man, was it ever.

Liz Ronk, who edited this gallery, is the Photo Editor for LIFE.com. Follow her on Twitter at @LizabethRonk.

Lucille Ball, 1942. An outtake from John Florea's 1942 photo essay on Ball, which touted her as being on the brink of fame after a decade of kicking around Hollywood.

Lucille Ball, 1942

John Florea The LIFE Picture Collection/Getty Images

Lucille Ball, 1942.

Lucille Ball, 1942

John Florea The LIFE Picture Collection/Getty Images

Lucille Ball in costume for the extravagant dream sequence set in 18th-century France at the center of DuBarry Was a Lady, 1943.

Lucille Ball, 1943

Walter Sanders The LIFE Picture Collection/Getty Images

Lucille Ball plays upon her modeling past for Lured, a comic thriller in which she starred as a woman who agrees to pose as bait for a serial killer, 1946.

Lucille Ball, 1946

Bob Landry The LIFE Picture Collection/Getty Images

Lucille Ball signs autographs for admiring seamen at one of the January 1944 galas celebrating President Franklin D. Roosevelt's 62nd birthday.

Lucille Ball, 1944

Thomas D. McAvoy The LIFE Picture Collection/Getty Images

Lucille Ball performs at one of the gala balls in Washington marking President Franklin D. Roosevelt's birthday in January 1944.

Lucille Ball, 1944

Thomas D. McAvoy The LIFE Picture Collection/Getty Images

Lucille Ball, 1944.

Lucille Ball, 1944

Thomas D. McAvoy The LIFE Picture Collection/Getty Images

Lucille Ball has her hair done, 1944.

Lucille Ball, 1944

Thomas D. McAvoy The LIFE Picture Collection/Getty Images

Lucille Ball

Lucille Ball, 1944

Thomas D. McAvoy The LIFE Picture Collection/Getty Images

Lucille Ball, 1944.

Lucille Ball, 1944

Thomas D. McAvoy The LIFE Picture Collection/Getty Images

In 1958, on the set of The Lucy-Desi Comedy Hour   a collection of occasional, lavish specials that followed the adventures of the Ricardos and the Mertzes after I Love Lucy -- Lucille Ball does a comedy bit as a wisecracking clerk.

Lucille Ball, 1958

Leonard McCombe The LIFE Picture Collection/Getty Images

Lucille Ball and Desi Arnaz

Lucy and Desi, 1958

Leonard McCombe The LIFE Picture Collection/Getty Images

Lucille Ball is a calm eye at the center of a storm of activity at her new Desllu Studios, 1958.

Lucille Ball, 1958

Leonard McCombe The LIFE Picture Collection/Getty Images

Lucille Ball and Desi Arnaz

Desi Arnaz and Lucille Ball, 1958

Leonard McCombe The LIFE Picture Collection/Getty Images

Lucille Ball and Desi Arnaz

Desi Arnaz and Lucille Ball, 1958

Leonard McCombe The LIFE Picture Collection/Getty Images

Lucille Ball plays a matador, 1958

Lucille Ball, 1958

Leonard McCombe The LIFE Picture Collection/Getty Images

Desi Arnaz and Lucille Ball, 1958.

Desi Arnaz and Lucille Ball, 1958

Leonard McCombe The LIFE Picture Collection/Getty Images

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