Officers responded to the two-car crash just after 12:30 p.m. Wednesday in northern Indiana.
Law enforcement initially said a car driving northbound drifted left of the center line and struck an SUV traveling southbound head on.
But they said after finding eyewitness and video evidence, they learned the Buick LeSabre was traveling south and the Toyota RAV4 SUV north before crossing the centerline for unknown reasons.
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Walorski was in the SUV along with St. Joseph County Republican Chair Zachery Potts, 27, and staff member Emma Thomson, 28. All three were killed. The driver of the car, 56-year-old Edith Schmucker, was also killed, the sheriff's office said.
All occupants of both vehicles were confirmed to have been wearing seatbelts, and airbags did deploy, police said.
An investigation into the crash is ongoing.
Republican House Minority Leader Kevin McCarthy shared a statement from Walorski's office that reads, "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. She has returned home to be with her Lord and Savior, Jesus Christ. Please keep her family in your thoughts and prayers. We will have no further comment at this time."
Democratic Congressman Danny Davis served on the House Ways and Means Committee with Walorski.
"I was almost in a state of shock. I couldn't believe it," he said. "We might disagree from time to time, but I don't think we ever had an argument. She was a wonderful person to work with."
Indiana Senator Mike Braun also spoke fondly about his fellow lawmaker.
"Spent a lot of time with Jackie, got to her know her when I stuck my neck into the political realm, and always a good friend and she was a tireless congresswoman," he said.
Walorski has represented Indiana's 2nd district since 2012.
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President Joe Biden released a statement on her death, saying in part, "We send our deepest condolences to her husband, Dean, to the families of her staff members, Zachery Potts and Emma Thomson, who lost their lives in public service, and to the people of Indiana's Second District who lost a representative who was one of their own."
House Speaker Nancy Pelosi ordered flags at the Capitol to be flown at half-staff in response to the death of the congresswoman, Pelosi deputy chief of staff Drew Hammill announced Wednesday afternoon.
In a statement, Pelosi said the congresswoman "lived a life of service" and "was admired by colleagues on both sides of the aisle for her personal kindness."
Illinois GOP Rep. Darren LaHood released a statement saying, "Over the years, Jackie and I, and our staffs, worked closely together on important Ways and Means issues to help our Midwest communities. Jackie and her staff were a joy to work with and there was no more dedicated Member of Congress."
Illinois Democrat Rep. Brad Schneider released a statement saying, "I am heartbroken at the passing of Rep. Walorski, Zachary Potts, and Emma Thomson. My heart goes out to all of their families, friends, and colleagues. Jackie was a good friend and esteemed colleague who I had the good fortune to work with. May the memories of all be a blessing."
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House Minority Whip Steve Scalise said in a statement that Walorski "was a champion for the people of Indiana, and she will be remembered for her kindness, tenacity, and commitment to helping others."
The congresswoman served as the top Republican on the House Ethics Committee, a spot that put her in line to become chair of the panel if the GOP retakes the House majority in the upcoming midterm elections. She also served as the ranking GOP member for a subcommittee of the powerful House Ways and Means committee.
GOP Rep. Liz Cheney of Wyoming tweeted in reaction to the news, "There was no more dedicated or effective member of Congress than Jackie," adding, "I was proud to be her friend."
The sheriff's office asked that anyone with information on the crash, or who witnessed it, reach out.
The CNN Wire contributed to this report