In November 1814, Miller was elected Governor of North Carolina by the General Assembly, at the close of the War of 1812, which he supported. During his term, Miller laid the groundwork for the expansion of the state's educational system, and he served on the University of North Carolina Board of Trustees until his death.
After serving the maximum number of three one-year terms as governor, Miller left office in 1817. He returned to the North Carolina Senate in 1821, but lost a re-election bid the following year.
^"Appointments by the President and Senate". Aurora and Franklin Gazettez. Vol. XV, no. 2162. Number 6 Bank Alley, Philadelphia. March 14, 1825. p. 2. William Miller, of North Carolina, to be Charge des Affaires to the Central Republic of America, Guatemala{{cite news}}: CS1 maint: location (link)
^"News item". Raleigh Register and North-Carolina State Gazette. Vol. XXIV, no. 1359. October 21, 1825. p. 3. By an arrival at Norfolk, direct from Key West, intelligence is received of the death of William Miller, Esq'r. Charge des Affaires to Guatemala, and formerly Governor of this State, after three days illness. It would appear, that he had not reached Guatemala, but was still waiting at Key West for a vessel. This is the second appointment on that embassy, and in both instances the gentlemen selected were from this State, but neither of them ever reached their destined post.
Biographical Directory of the Governors of the United States, 1789–1978, Robert Sobel and John Raimo, eds. Westport, CT: Meckler Books, 1978. (ISBN0-930466-00-4)