Mathews was born in Charleston in the Province of South Carolina in 1744. He was the son of John Mathews and Sarah Gibbes; the exact date of his birth is not known. He was commissioned an ensign and in the South Carolina Provincial Regiment which took part in an expedition against the Cherokee in the early 1760s and was promoted to lieutenant.[1]
He studied law at Middle Temple in London. He was a law clerk for Colonel Charles Pinckney after returning to South Carolina, was admitted to the bar, and practiced in Charleston. In 1772, he was elected to the colonial Assembly. In 1775 and 1776, he was a member of the First and Second South Carolina Provincial Congresses.[2] In 1776, he was appointed an associate judge of the state circuit court. From 1776 to 1780, he served in the South Carolina House of Representatives, and he was speaker in 1777 and 1778. During the American Revolutionary War, he served as a captain in the Colleton County regiment. He was a founding trustee of the College of Charleston.
Mathews was a member of the Continental Congress from 1778 to 1781 and was a supporter of the Articles of Confederation. He was then elected governor by the state legislature and served from 1782 to 1783. After leaving the governorship, Mathews won election as a judge of the state Court of Chancery in 1784. He was again elected to the South Carolina House in 1784. He was a judge of the state Court of Equity in 1791.