In 1788, he served in the State house of representatives. He became a member of the Massachusetts convention called for the ratification of the Federal Constitution in 1788.
Ames was elected to the First, Second and Third Congresses and as a Federalist to the Fourth Congress. He served the Congress from March 4, 1789 to March 3, 1797. During the First Congress, he was chairman of the Committee on Elections. in 1796, he was not a candidate for renomination but resumed the practice of law in Dedham. He stayed in politics and was member of the Governor's council from 1798 to 1800.
In 1804, Ames was chosen president of Harvard University. He declined to accept because of failing health. Four years later, in 1808, he died in Dedham on July 4. He was intered in the Old First Parish Cemetery.
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