In 1831 he moved to Cincinnati, Ohio, where after a year spent in the law office of Bellamy Storer and Charles Fox he was admitted to the bar and joined a practice with the politician Edward King.[2] They were joined in this partnership by another young Cincinnati lawyer, Salmon P. Chase, who left the firm after a few months to pursue his interest in banking law. Around this time Walker and Chase joined a literary salon, the Semi-Colon Club, where Walker met his first wife, Anna Lawler Bryant, the granddaughter of Matthew Lawler.[3]
In 1833, Walker, along with King and John C. Wright, founded the Cincinnati Law School. At the time there were only six other law schools in the country, and it was the first law school in the West. Walker served as Dean, and continued in that position when the school merged with Cincinnati College in 1835. He was Dean 1833 to 1844.[4]
Walker was President Judge of the Hamilton CountyCourt of Common Pleas, founded the Western Law Journal in 1843, and was its editor. His Introduction to American Law (1837, revised several times) was for many years "the most generally used text-book in the country".[5] This book earned him the title "The American Blackstone".[4] Walker wrote a number of other historical and legal books.[2] He was given the degree LL.D. by Harvard in 1854,[5] and was the Phi Beta Kappa orator at that institution in 1850.[6]