Wells was educated at the Jesuit-run St. Joseph's College in Bardstown south of Louisville, Kentucky; Partridge's Academy, Middletown, Connecticut; and Cincinnati Law School.

Wells inherited a substantial estate; he controlled a large cotton plantation called New Hope near Alexandria, a sugar plantation on Bayou Huffpower in Avoyelles Parish called Wellswood, and a large summer home Jessamine Hill near Lecompte, Louisiana.

[citation needed] Wells remained on his plantation outside Alexandria until the spring of 1863 when he remarked that the recently deceased Gen. "Stonewall" Jackson should be buried "in a gum coffin, and that the bottom plank might be very thin, so that he might eat his way down to where it was intended that he should go."

Soon thereafter, he fled into the woods and briefly organized a band of unionist partisans, or Jayhawkers, to attack rebel supply trains.

One year later, on March 4, 1865, Wells was inaugurated as governor when Michael Hahn resigned to become a United States Senator.

[citation needed] Wells came into conflict with the federal military authority under General Nathaniel P. Banks.

[citation needed] Governor Wells did little to prevent violence, and General Philip Sheridan held him responsible.

In 1873, he was appointed chairman of the State Returning Board, which was responsible for determining the legality of ballots and for discarding fraudulent votes.

In this, Wells helped Republicans regain some of the votes it lost to white Democrats' anti-Black violence and terror.