According to Bob Allen's book George Jones: The Life and Times of a Honky Tonk Legend, Jones first heard the song when Jack Clement played it for him at Gulf Coast Studio in Beaumont, which Clement owned with Bill Hall. The song had been written by Dickie Lee Lipscomb and Steve Duffy, two professional songwriters under contract to Clement's publishing company, so Clement was eager for Jones to record it. According to Allen, Jones had little interest, responding, "I don't like it too much. It's got too many damn 'just becauses' in it. I don't think nobody really wants to hear that shit, do you?" Undeterred, both Clement and Hall continued to pitch the song to Jones. Raymond Nalley, brother of Gulf Coast session musician Luther Nalley, later recalled:
"They had this ole, wornout, rinky-dink tape recorder layin' around the studio...Everytime they'd try to lay that song on George, he'd just look at that damn tape recorder and ask 'em, 'How much you sell me that thing for?' One day, Bill Hall finally told him, 'Hell, George, if you'll record the song, I'll give ya the damn tape recorder!'"
In his essay for 1994 Sony retrospective The Essential George Jones: The Spirit of Country, Rich Kienzle also states that Jones was underwhelmed by the song after Clement had "decided not to play George the tape but to sing him the song, altering the melody as he sang it to give it a stronger country feel." Jones himself always insisted he had no doubts about the song. Recalling his first impression of the tune, he insisted in the 1989 documentary Same Ole Me, "Boy, I just flipped! I said, 'Golly, lemme have this thing.'" In the 1994 video retrospective Golden Hits, he added, "It knocked me out. I couldn't wait to get into the studio." The song was released in April 1962, his first single release on United Artists after leaving Mercury, and it remained on the Billboard survey for twenty-three weeks, six of them at #1. In his autobiography I Lived to Tell It All, the singer wrote, "For years after I recorded it, the song was my most requested, and it became what people in my business call a 'career record,' the song that firmly establishes your identity with the public." The B-side, "Sometimes You Just Can't Win", reached No. 17 on the C&W chart. "She Thinks I Still Care" was one of seven records George would chart in 1962, and in the fall of 1963 he would travel to New York City and perform the song on Jimmy Dean's ABC network show.
Connie Francis recorded the song as "He Thinks I Still Care" in a June 18, 1962, session at Columbia Recording Studio in Nashville, Tennessee, which was produced by Danny Davis and Jim Vienneau. The track had a September 1962 single release as the B-side to "I Was Such A Fool (To Fall In Love With You)" but garnered enough attention to reach No. 57 on the Billboard Hot 100 (No. 51 on the Cash Box Pop 100).