Barry Manilow is to open and close the concert broadcast with a medley of hits and patriotic classics, along with the National Symphony Orchestra and the Choral Arts Society of Washington.
The July 4 celebration on the West Lawn of the United States Capitol is also to feature appearances by Aretha Franklin, Natasha Bedingfield, the cast of "Jersey Boys," Michael Feinstein and Andrew von Oeyen.
Elmo, Big Bird, Cookie Monster, Oscar the Grouch and more of the "Sesame Street" gang will be on hand as well to celebrate America's 233rd birthday.
The program, which is to culminate in a spectacular fireworks display, is slated to be broadcast live in high definition and commercial free on PBS.
"I am honored to be asked once again to host this year's special party to celebrate our great country's birthday ... and what a 'guest list,'" Smits said in a statement. "The music itself embraces so many genres -- we've got pop, we've got classical and we've got soul. Throw in an anniversary celebration of 'Sesame Street,' topped off with the biggest fireworks display around and we've got quite a show."
Smits is best known for his roles on the classic TV shows "The West Wing," "NYPD Blue" and "L.A. Law."