Jouett was among the ten men founding the town of New Market at the confluence of the Dick's and Kentucky Rivers. Shortly after Jouett moved to Kentucky, the large county was divided into Lincoln, Jefferson and Mercer Counties. Lincoln County voters elected Jouett as their representative in the Virginia House of Delegates (alongside Benjamin Logan). Jouett served one term from Lincoln County (October 16, 1786 – January 11, 1787) before Mercer County's creation, then one term from Mercer County (alongside William MacDowell from October 15, 1787 – January 8, 1788) before local voters replaced both by Samuel Taylor and Alexander Robinson. Jouett again won election to the Virginia House of Delegates from Mercer County in 1790, this time serving alongside Anthony Crockett from October 18 – December 29, before voters replaced both delegates with Samuel Taylor and Jacob Fromm.