After receiving his journalism degree in 1956, he spent a year at the University of Edinburgh in Scotland on a Rotary International fellowship. In 1957 he entered the Southwest Baptist Theological Seminary, earning a divinity degree and becoming an ordained minister in 1959. He briefly accepted a lectureship in Christian ethics at Baylor University. "I thought it was a call to the ministry," Moyers later told one interviewer, "but actually it was a wrong number."
Senator Lyndon Johnson invited Moyers to work on his 1960 presidential campaign. When Johnson eventually was named to be John F. Kennedy's vice presidential running mate, Moyers became LBJ's executive assistant.
After Kennedy was elected President, Moyers in 1961 became associate director of public affairs, and then deputy director, of JFK's new Peace Corps. After Kennedy's assassination in November 1963, Moyers rushed to Lyndon Johnson's side and became the new President's special assistant.
In LBJ's White House, Moyers supervised the task forces that shaped the legislation of the vast welfare expansion known as the Great Society. Moyers also orchestrated the 1964 political campaign of calculated defamation against Republican Senator Barry Goldwater of Arizona. Moyers personally green-lighted the notorious "daisy ad" that featured a little girl plucking daisy petals as a countdown leads to her vaporization in a nuclear blast, presumably what would happen if Goldwater were elected.
In 1965 Moyers was promoted to the position of President Johnson's Press Secretary. In 1967, however, Moyers and Johnson had a personal falling out and they never spoke to one another again.
Thereafter Moyers was named publisher of the suburban New York newspaper Newsday. Moving the publication farther to the political left, he turned it into a literary salon that invited writers such as Saul Bellow to be its correspondents. Moyers left in 1970 when Newsday was acquired by the then-conservative Los Angeles Times.