Jones was a member of the Democratic party and served in the Senate from 1848 to 1859, and was unsuccessful in an attempt to be renominated.
Jones was appointed as Minister Resident of the United States to New Granada in 1859. Upon returning to the United States in 1861, Jones was arrested by order of Secretary of State William Seward on the charge of disloyalty, based upon correspondence with his friend Jefferson Davis. Jones was held for sixty-four days, until he was released by order of President Abraham Lincoln.
Jones County, Iowa was named in honor of George W. Jones.