Wolcott opened a law office in Boston in 1875. He became increasingly involved in the affairs of his father's business associates, eventually being appointed to serve on a number of corporate boards. Businesses he was associated with included the Boston and Albany Railroad and the New England Trust Company. He was also involved in philanthropic organizations, serving as a member of the Boston Provident Association, and as trustee of the Eye and Ear Infirmary and the Massachusetts General Hospital. He was a member of the Massachusetts Historical Society, and an overseer of Harvard College.