At the seventh event in the "In Performance at the White House" series, the president said he and first lady Michelle Obama were "transforming the East Room into a bona fide country music hall."
"As Charley Pride, who played here two years ago, once said: 'There is enough room in country music for everybody,'" he said.
The lineup of performers Monday also included James Taylor and The Band Perry.
Kristofferson, Lovett and singer Darius Rucker joined the first lady Monday afternoon in conducting a workshop on the history of country music for young musicians.
"It is a proud history that runs from barn stomping to the great honky tonks to the big stage to the GRAMMYs," the president said. "It's a unique history that ties together many threads of our immigrant heritage -- like the Irish fiddle, the German dulcimer, the Italian mandolin, the Spanish guitar and the West African banjo -- into music that is truly Made in America. And at its most pure, that's what country music is all about -- life in America."
Previous "In Performance at the White House" events celebrated jazz, classical, Broadway, R&B and Latin music.
Monday's performance was streamed live on the White House Web site and is scheduled to be televised on PBS stations Wednesday.