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- William Walker (filibuster) (1824–1860), American filibuster or pirate in Latin America; briefly ruled Nicaragua
- William Walker, 1st Baron Wavertree (1856–1933), British businessman, art collector, and racehorse breeder
- William Walker (diver) (1869–1918), diver who saved Winchester Cathedral from collapse
- William F. Walker (1937–2007), President of Auburn University (2001–2007)
- William Hultz Walker (1869–1934), American chemistry professor and a pioneer of chemical engineering discipline
- William R. Walker (born 1944), Canadian leader in The Church of Jesus Christ of Latter-day Saints
- William R. Walker (publisher), 19th century English printer and publisher
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