John Quincy Adams was the very able Secretary of State for Monroe.
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James Buchanan, who served as Secretary of State for James Polk was the most recent Secretary of State to later become President. (Other former Secretaries who later became President were Martin Van Buren, John Quincy Adams, James Monroe , James Madison and Thomas Jefferson.)
I count six -- Jefferson, Madison, Monroe, Quincy Adams, VanBuren and Buchanan were Secretaries of State before being elected president.
No ex-president has later become a Secretary of State- six have moved up from Secretary of State to president, however.
The first cabinet officer in line for the presidency is the Secretary of state, who is behind the vice-president, the Speaker of the House and president pro tempore of the Senate.
Congress approves Secretary of State.