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Rock stars Sting and Sam Moore will also appear at the event, which will raise funds for arts and entertainment advocacy group The Creative Coalition.
Anne Hathaway, Susan Sarandon, Marcia Cross and film director Spike Lee will also appear at the sold-out event.
Other confirmed guests include British actor Alan Cumming and singer Seal.
West Wing star Richard Schiff will also attend, alongside members of the US Congress and policy and business leaders.
Cable show
Musical guests are scheduled to perform until midnight at the event, to take place in Washington's Harman Center of the Arts.
Costello and Sting are making a habit of sharing the same stage, having recently appeared in an opera together at the Chatelet Theatre in Paris.
The British singers trod the boards in Welcome to the Voice, co-written by Costello's keyboardist Steve Nieve, in November.
Costello can currently be seen on US TV screens presenting Spectacle, a cable show that sees him discussing and performing music with celebrity guests.
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