Former Wimbledon champion Rybakina is joined by fellow top-10 players Amanda Anisimova and Victoria Mboko in the women’s singles, along with French Open semi-finalist Marta Kostyuk.
Raducanu was the only Briton to gain direct entry into the draw, with wildcards given to Katie Boulter, Francesca Jones, Harriet Dart and teenager Mika Stojsavljevic.
Williams, who has been granted a wildcard for the tournament, will play alongside Canadian teenager Mboko in the women’s doubles.
The 44-year-old said she would be “evolving away” from tennis in 2022 but has decided to return, saying Queen’s Club “feels like the perfect place to begin this next chapter”.
Wimbledon, where Williams has won seven singles and seven doubles titles, begins three weeks after Queen’s.
Lorenzo Musetti, Jiri Lehecka, Luciano Darderi and Valentin Vacherot are the other top 20-ranked players in the men’s singles draw alongside De Minaur.
Rising stars Jakub Mensik and Rafael Jodar are also in action.