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The cyclist and the Dexter star, both cancer survivors, will appear on September's Stand Up To Cancer programme along with Christina Applegate, Maura Tierney and Robin Roberts.
The telecast will also feature musical performances from Natasha Bedingfield, Queen Latifah and Stevie Wonder as well as testimonials from other actors, musicians, and athletes.
A previous edition of the TV fundraiser aired in 2008 and raised more than $100 million for cancer research.
Stand Up To Cancer will air commercial-free across ABC, CBS, Fox and NBC on September 10.
