The congresswoman had been traveling down an Indiana road on Wednesday afternoon with her communications chief, Emma Thomson, 28, and one of her district directors, Zachery Potts, 27, the Elkhart County Sheriff's Office said.
"A northbound passenger car traveled left of center and collided head on" with Walorski's vehicle, killing all three occupants, the sheriff's office said. The driver of the other car, 56-year-old Edith Schmucker, was pronounced dead at the scene, near the northern Indiana town of Nappanee, it added.
Confirming her death in a statement shared on Twitter by House Republican leader Kevin McCarthy, Walorski's office said: "Dean Swihart, Jackie's husband, was just informed by the Elkhart County Sheriff's office that Jackie was killed in a car accident this afternoon."
It added: "Please keep her family in your thoughts and prayers. We will have no further comment at this time."
Walorski was a lifelong resident of Indiana, according to her official biography. She served on the House Ways and Means Committee and was the top Republican on the subcommittee on worker and family support.
Prior to her election in 2012 to the House, Walorski served three terms in the Indiana legislature, spent four years as a missionary in Romania along with her husband and worked as a television news reporter in South Bend, according to a biography posted on her congressional website.
President Joe Biden, a Democrat, said he and Walorski "may have represented different parties and disagreed on many issues, but she was respected by members of both parties for her work on the House Ways and Means Committee on which she served."
Nancy Pelosi, the Democratic speaker of the House, said in a statement that Walorski "passionately brought the voices of her north Indiana constituents to the Congress, and she was admired by colleagues on both sides of the aisle for her personal kindness."