Holmes and actor Gary Sinise are among the stars confirmed for the event, set for Sunday, May 24.
The wife of Tom Cruise along with actress Dianne Weist will team up to read one veteran's personal story. Those readings have been based on veterans' letters home in past concerts.
The concert will include appearances by Laurence Fishburne, Katharine McPhee, Trace Adkins, former Secretary of State Colin Powell and Broadway stars Brian Stokes Mitchell and Colm Wilkinson.
The show will be broadcast live on PBS.
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