The 14th president of the US was Franklin Pierce. He was also a Senator and a member of the House of Representatives but never a vice president. There were nine presidents who were also vice presidents. They were Tyler, Fillmore, Andrew Johnson, Arthur, Theodore Roosevelt, Coolidge, Truman, Lyndon Johnson, and Ford.
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The Vice President is the President of the Senate.
The person who serves as President of the Senate, is also vice president of the United States of America.
I think it may be the President pro tempore, as he is third in line if the President and the Vice President are killed or incapacitated.
It is also the duty of the vice president to preside over the Senate.
Of the 14 U. S. Vice Presidents who became President, the only one whose presidency did not immediately follow his vice presidency is Richard M. Nixon. He did run for president while still the incumbent vice president, but he lost that election (1960) and did not run again for president until 8 years later. It's interesting that Nixon preceded Lyndon Johnson as vice president, but Johnson preceded Nixon as president.