Titled "God is Love," the watercolor of the late Pulitzer Prize-winning jazz great Duke Ellington is the third of Bennett's works to be accepted as part of the Smithsonian collection.
In 2006, Bennett's oil painting of Central Park was accepted into the Smithsonian American Art Museum's permanent collection and in 2002, his portrait of Ella Fitzgerald was acquired by the Smithsonian's National Museum of American History.
The 82-year-old performer is a 15-time Grammy Award-winner. Both he and Ellington were raised in Queens, N.Y.
"We are thrilled to have this painting," Martin Sullivan, director of the National Portrait Gallery, said in a statement. "Think of it: Anthony Benedetto -- Tony Bennett -- the son of Italian immigrants, portraying his mentor Duke Ellington, the grandson of a slave. There was great affection between these two outstanding contributors to America's musical heritage."
"It is an enormous honor to now have three of my paintings in collections at the Smithsonian and it is something that I would never have imagined when I started out as a young child drawing with chalk on the sidewalks of my hometown in Astoria, Queens," added Bennett. "Painting has been a lifelong passion of mine and the portrait of Duke Ellington is my favorite painting of all and it is a thrill to know it will have a permanent home at such a prestigious institution as the National Portrait Gallery."