In June 1952, he recorded "Jambalaya (On the Bayou)", "Window Shopping", "Settin' the Woods on Fire", and "I'll Never Get out of this World Alive". Audrey Williams divorced him that year; the next day he recorded "You Win Again" and "I Won't be Home No More". Around this time, he met Billie Jean Jones, a girlfriend of country singer Faron Young, at the Grand Ole Opry. As a girl, Jones had lived down the street from Williams when he was with the Louisiana Hayride, and now Williams began to visit her frequently in Shreveport, causing him to miss many Grand Ole Opry appearances.
On August 11, 1952, Williams was dismissed from the Grand Ole Opry for habitual drunkenness and missing shows. He returned to Shreveport, Louisiana to perform on KWKH and WBAM shows and in the Louisiana Hayride, for which he toured again. His performances were acclaimed when he was sober, but despite the efforts of his work associates to get him to shows sober, his abuse of alcohol resulted in occasions when he did not appear or his performances were poor. In October 1952 he married Billie Jean Jones.
During his last recording session on September 23, 1952, Williams recorded "Kaw-Liga", along with "Your Cheatin' Heart", "Take These Chains from My Heart", and "I Could Never be Ashamed of You". Due to Williams' excesses, Fred Rose stopped working with him. By the end of 1952, Williams had started to suffer heart problems. He met Horace "Toby" Marshall in Oklahoma City, who said that he was a doctor. Marshall had been previously convicted for forgery, and had been paroled and released from the Oklahoma State Penitentiary in 1951. Among other fake titles, he said that he was a Doctor of Science. He purchased the DSC title for $25 from the Chicago School of Applied Science; in the diploma, he requested that the DSC be spelled out as "Doctor of Science and Psychology". Under the name of Dr. C. W. Lemon he prescribed Williams with amphetamines, Seconal, chloral hydrate, and morphine, which made his heart problems worse. His final concert was held in Austin, Texas at the Skyline Club on December 19.
In June 1952, Williams moved in with his mother, even as he released numerous hit songs, such as "Half as Much" in April, "Jambalaya (On the Bayou)" in July, "Settin' the Woods on Fire"/"You Win Again" in September, and "I'll Never Get Out of This World Alive" in November. His substance abuse problems continued to spiral out of control as he moved to Nashville and officially divorced his wife. A relationship with a woman named Bobbie Jett during this period resulted in a daughter, Jett Williams, who was born five days after Williams' death. His mother adopted Jett, who was made a ward of the state and then adopted by another couple after her grandmother died. Jett Williams did not learn that she was Hank Williams' daughter until the early 1980s.
On October 18, 1952, Williams and Billie Jean Jones Eshlimar were married in Minden, Louisiana by a justice of the peace. It was the second marriage for both (each being divorced with children). The next day, two public ceremonies were also held at the New Orleans Civic Auditorium, where 14,000 seats were sold for each. After Williams' death, a judge ruled that the wedding was not legal because Jones Eshlimar's divorce had not become final until 11 days after she married Williams. Williams' first wife, Audrey, and his mother, Lillie Williams, were the driving forces behind having the marriage declared invalid and pursued the matter for years. Williams had also married Audrey Sheppard before her divorce was final, on the 10th day of a required 60-day reconciliation period.
In the 1952 presidential election campaign, Williams was a vocal supporter of General Dwight D. Eisenhower, the Republican party nominee. According to singer and recording artist Jo Stafford, Williams sent Eisenhower a birthday telegram on October 14 informing him that he considered it a personal honor to endorse a military figure to lead the nation in its coming future. Eisenhower was sworn in as the 34th president 19 days after Williams' death.
His final single, released in November 1952 while he was still alive, was titled "I'll Never Get Out of This World Alive". "Your Cheatin' Heart" was written and recorded in September 1952 but released in late January 1953 after Williams' death. The song, backed by "Kaw-Liga", was number one on the country charts for six weeks. It provided the title for the 1964 biographical film of the same name, which starred George Hamilton. "Take These Chains From My Heart" was released in April 1953 and went to number 1 on the country charts. "I Won't Be Home No More", released in July, went to number 3, and an overdubbed demo, "Weary Blues From Waitin'", written with Ray Price, went to number 7.