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.
The Secretary of State is fourth in line following the Vice President, the Speaker of the House, and the President Pro Tempore of the Senate.
James Madison was the President for whom Monroe served as Secretary of State. (He also served as Madison's Secretary of War for a year or so.)
James Monroe served as Secretary of State and as Secretary of War under Madison. For some of the time, he held both positions at once.
James Madison was the President for whom Monroe served as Secretary of State. (He also served as Madison's Secretary of War for a year or so.)
John Quincy Adams was the very able Secretary of State for Monroe.
Robert Smith and James Monroe
Madison
James Monroe is the man. He went on to become the next President.
John Adams
James Monroe held both of these two positions for a year or so under President James Madison. He served as Secretary of State for all of Madison's administration.
James Monroe, the Fifth US President was the Seventh Secretary of State and the Eigth Secretary of War.
John Quincy Adams
James Monroe served as Secretary of War, as well as Secretary of State for James Madison. (Confederate President Jefferson Davis was Secretary of War for Franklin Pierce)