Riley, who plays Effie White, and LaFontaine, who plays Deena Jones, will perform the song "Listen", at the concert, which take place at the Prince of Wales Theatre on 19 February. The WhatsOnStage Awards are the only major theatre awards in which the audience votes for the winners.
Dreamgirls is a musical by Henry Krieger and Tom Eyen and is based on the success of acts including James Brown, The Shirelles and The Supremes. The West End production, which opened in December, is directed and choreographed by Casey Nicholaw.
Riley, who is also a judge on Gary Barlow's new TV talent show Let it Shine, has been nominated in this year's awards for Best Actress in a Musical. She is up against Carrie Hope Fletcher for Chitty Chitty Bang Bang, Devon-Elise Johnson for Half a Sixpence, Glenn Close for Sunset Boulevard and Sheridan Smith for Funny Girl.
Dreamgirls has been nominated in other categories including Best Supporting Actor in a Musical for Adam J Bernard, Best New Musical and Best Choreography.
Riley and LaFontaine join the already announced Tyrone Huntley, Ria Jones and School of Rock, as appearing at the WhatsOnStage Awards. Voting has now closed for the awards winners.
The 17th Annual WhatsOnStage Awards take place at the Prince of Wales Theatre on 19 February.
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