The brothers adopted the name Louvin Brothers in the 1940s as they began their career in gospel music. Their first foray into secular music was the minor hit "The Get Acquainted Waltz", recorded with Chet Atkins. Other hits included "Cash on the Barrelhead" and "When I Stop Dreaming". They joined the Grand Ole Opry in 1955 and stayed there until breaking up in 1963.
Their songs were heavily influenced by their Baptist faith and warned against sin. Nevertheless, Ira Louvin was notorious for his drinking, womanizing, and volcanic temper. He was married four times; his third wife Faye shot him four times in the chest and twice in the hand after he allegedly tried to strangle her with a telephone cord. Although seriously injured, he survived. (Faye is reported to have said, "if the bastard don't die I'll shoot him again!"). When performing and drinking, Ira would sometimes become angry enough on stage to smash his mandolin when he was unable to tune it, and - when sober - glue it back together. His style was heavily influenced by Bill Monroe, and his brother Charlie Monroe, who had a tempestuous relationship with Ira, considered him one of the top mandolin players in Nashville.
In his New York Times review of Charlie's biography Satan Is Real, Alex Abramovich said, "Ira Louvin was a full head taller than his younger brother, played the mandolin like Bill Monroe and sang in an impossibly high, tense, quivering tenor. Charlie strummed a guitar, grinned like a vaudevillian and handled the bottom register. But every so often, in the middle of a song, some hidden signal flashed and the brothers switched places — with Ira swooping down from the heights, and Charlie angling upward — and even the most careful listeners would lose track of which man was carrying the lead. This was more than close-harmony singing; each instance was an act of transubstantiation."
In 1963, fed up with Ira's drinking and abusive behavior, Charlie started a solo career, and Ira also went on his own.
Ira died on June 20, 1965, at the age of 41. He and his fourth wife, Anne Young, were on the way home from a performance in Kansas City when they came to a section of construction on Highway 70 outside of Williamsburg, Missouri where traffic had been reduced down to one lane. A drunken driver struck their car head-on, and both Ira and Anne were killed instantly.  At the time, a warrant for Ira's arrest had been issued on a DUI charge.
Charlie died of pancreatic cancer on January 26, 2011 at age 83.