Huntsman was born in Charlotte County, Virginia, on February 11, 1786. He came to Knox County, Tennessee, in 1809, where he settled for about three years. It was here that he studied law under John Williams, one of Knoxville's most prominent attorneys in the early nineteenth century and later a United States Senator.
Huntsman served in the Tennessee state senate from 1815 to 1821 and from 1827 to 1831. A proponent of revision to the state constitution, he was elected a delegate for Madison County, Tennessee, at the constitutional convention held in Nashville, Tennessee, in 1834. He defeated David Crockett for the Twelfth Congressional seat in 1835, a loss that led to Crockett's journey to Texas and his death at the Alamo.
Huntsman served one term as a Jacksonian Democrat to the Twenty-fourth Congress. A leader of the Democratic Party in West Tennessee in the 1830s and 1840s, he corresponded with notable politicians of his day such as Andrew Jackson, James K. Polk, James Buchanan, and John C. Calhoun. His term lasted from March 4, 1835, to March 4, 1837. He ran unsuccessfully for re-election to the Twenty-fifth Congress, losing to John Wesley Crockett, his predecessor's son.