In 1799, he entered Latin school, but soon his education was taken over by his paternal grandfather, Reverend William Smith—who had been the first provost of the College of Philadelphia.

[1] In 1803, his father, William Moore Smith, was appointed one of the commissioners to England to negotiate the ongoing adjustments and claims related to the "Jay Treaty" of 1795.

In 1808, he was admitted to the Pennsylvania Bar and moved to Huntingdon, Pennsylvania—a town that had been laid out by his grandfather—where he started his legal practice.

[7] That same year, as he continued his legal career, he was admitted to the bar of the Supreme Court of the United States.

[2] On March 25, 1837, Smith was appointed commissioner for the United States, along with Wisconsin Territory Governor Henry Dodge, to negotiate with the Chippewa to purchase Ojibwe lands.

[8] He arrived too late; Dodge had already single-handedly wrested old growth pine and millsites in the future east central Minnesota and central Wisconsin from the assembled Ojibwe by a treaty negotiated at Fort Snelling in late July 1837.

In 1846, Smith was hired as Clerk of the Legislative Council (the upper body of the territorial legislature) and, that same year, was elected as one of Iowa County's delegates to Wisconsin's first constitutional convention.

Smith defeated Republican candidate Alexander Randall, who, two years later, would be elected Governor.

Smith ultimately referred the matter to the Wisconsin Supreme Court on the information provided by Bashford that Barstow's majority relied on fraudulent returns.