Chamberlain won the 1902 Republican gubernatorial nomination, and was elected Connecticut's 43rd governor.

During his tenure, he signed legislation that sanctioned the establishment of the Connecticut State Police, and he endorsed laws that assisted workers.

[3] On February 1, 1903, he became the first Connecticut governor to deploy the National Guard against strikers, as part his response to the Waterbury Trolley Strike of 1903.

His response to station 17 infantry companies and two Gatling gun sections for four days in the city was criticized by Waterbury Mayor Edward G. Kilduff.

He is interred at Walnut Grove Cemetery, Meriden, New Haven County, Connecticut.