The 47-year-old pop star took the stage during the soirée on the South Lawn, where she performed her 2006 hit "The Sweet Escape" in front of an exclusive party of A-list guests, including First Lady Michelle Obama, Vice President Joe Biden, Giorgio Armani, Rachael Ray, Frank Ocean and Mario Batali, the latter of whom provided the event's gourmet cuisine.
Stefani was then joined on stage by Shelton, 40, for a performance of their duet "Go Ahead and Break My Heart." As the country singer played his guitar and looked dapper in a black tuxedo, his girlfriend stunned in a sheer black-and-silver dress with her long blonde locks pulled back in a ponytail.
The happy couple, who started dating in November 2015 (as Us Weekly exclusively revealed), were later spotted speaking with New York Governor Andrew Cuomo and his girlfriend, chef Sandra Lee.
Earlier in the day, the No Doubt frontwoman visited the White House with her three sons, Kingston, 10, Zuma, 8, and Apollo, 2. The foursome met with Italian Prime Minister Matteo Renzi and his wife, Agnese Landini, in addition to the U.S. commander in chief and first lady.
Stefani's performance Tuesday night amazed fellow attendee Chance The Rapper, who gushed on Twitter: "Gwen Stefani just sang to me at the White House. And pointed at me. Bro. I'm dead."
Chance, 23, attended the event with his father, Ken Bennett, who once worked for then–Senator Obama and is now a deputy chief of staff to Chicago Mayor Rahm Emanuel.
While getting ready to head to the state dinner, the "No Problem" MC tweeted a photo with his dad, writing, "Thanks Dad for raising me right. Look at us all fancy for the White House. I ain't even wearing a hat tonight #BlackBoyJoy."
Sign up now for the Us Weekly newsletter to get breaking celebrity news, hot pics and more delivered straight to your inbox!