- He made his film debut in How Green Was My Valley (1941), which takes place in rural Wales. The movie was actually filmed in Hollywood with a cast of English, Irish, Scottish and American actors. Originally hired solely to coach the actors in their Welsh accents, Williams, who was the only genuine Welshman on the set, was given the role of the prizefighter by director John Ford.
- He appeared in two consecutive Best Picture Academy Award winners: How Green Was My Valley (1941) and Mrs. Miniver (1942). Walter Pidgeon, Mary Field and Frank Baker also appeared in both films. Rhys Williams also appeared in three other Best Picture nominees: Random Harvest (1942), The Bells of St. Mary's (1945) and Julius Caesar (1953).
- Was technical advisor and actor in Ethel Barrymore's production of The Corn is Green.
- Interred at Forrest Lawn Memorial Park, Los Angeles.
- His first son died shortly after birth in 1941.
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