U.S. Senate and Peace Commissioner
Although re-elected to the U.S. House in 1804, Bayard never returned there, because before the term began, on November 13, 1804, he was elected by the Delaware General Assembly as U.S. Senator, filling the vacancy caused by the resignation of William H. Wells. He began a term of his own the following March 1805, was reelected six years later in 1810, and served in the Senate until his resignation on March 3, 1813.
By his admission, it mattered little who represented Delaware, given the smallness of the state; if the two senators and one representative happened to be all Federalists, all the better, since the party was in a considerable minority by the decade of the 1800s. Like most of his party, Bayard opposed "Mr. Madison's War" as the War of 1812 was sometimes scornfully called, but like the Democratic-Republicans, he was outraged at the British actions on the high seas and recognized the need for action. As the possibility of war became more likely, he urged caution, thinking of the lack of preparedness of the army and navy and especially of the vulnerability of coastal Delaware. On June 17, 1812, he was one of 13 senators to vote against declaring war on Britain. However, once the war began he and all Delaware Federalists wholeheartedly supported the war effort, avoiding the suspicion of treason earned by Federalists in New England.
Because of that support, he was the only Federalist appointed as one of the peace commissioners who eventually negotiated the Treaty of Ghent. Resigning his Senate seat, he went to Europe and played a major role in the negotiations that ended the War of 1812 when the treaty was signed in December 1814. John Quincy Adams, head of the American negotiating team, praised Bayard:Of the five members of the American mission, the Chevalier [Bayard] has the most perfect control of his temper, the most deliberate coolness; and it is the more meritorious because it is real self-command. His feelings are as quick and his spirits as high as those of any one among us, but he certainly has them more under government.Subsequently, President James Madison offered him an appointment as Minister to Russia, but Bayard declined, believing a Federalist could hardly represent a Democratic-Republican administration.
Bayard was elected a member of the American Antiquarian Society in July 1815. His disposition on membership is unknown, as no known correspondence confirms or denies his interest, and his death was only a few weeks after his election, and a few days after his return from Europe.