A native of North Carolina, Willie Blount studied at Princeton and Columbia. He later was admitted to the North Carolina bar. In 1790, he moved to the Southwest Territory and served as his half-brother's private secretary. When Tennessee was admitted as a state in 1796, he was one of its first judges, and in 1807 was elected to the Tennessee House of Representatives, 7th General Assembly, 1807-09; representing Montgomery and Stewart counties. He was elected governor in 1809, and served three terms, until 1815. During his governorship, he supported the War of 1812. He also sent Tennessee militia to Mississippi Territory when the latter was essentially defenseless before attacks by American Indians.

Blount attempted a political comeback in 1827, running for governor again, but was defeated by Sam Houston. He was a delegate to the state constitutional convention in 1834, which drafted a new document to replace the one in effect since the state had been admitted in 1796, and which has many similarities to the 1870 constitution which is still in effect. One of the chief differences between the 1834 constitution and its predecessor was considerably greater powers being granted to the executive branch generally and the governor in particular than in the earlier document.

Blount County, Alabama is named in his honor for his willingness to send the Tennessee militia into a neighboring territory.

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