Yes. Out of the 49 Vice Presidents there have been 13 Vice President's who have not served in Congress. Chester A Arthur and Garrett Hobart made the greatest leaps to the VP.

Jefferson- John Adams VP, when elected was a former Sec. of State

George Clinton- Jefferson's and Madison's VP and I believe the only person to serve as VP to two different Presidents. Clinton was Gov of NY prior to being VP.

Daniel Tompkins- Served as Monroe's VP and was Gov of NY prior to being VP.

Chester A Arthur- Served as Garfield's VP but made the biggest leap as Chair of the NY Republican Party to Vice President.

Garrett Hobart- Served as McKinley's VP and was President of the NJ Senate prior to becoming VP he died while in office.

T Roosevelt- Served as McKinley's VP after Hobert and was Gov of NY prior to becoming VP

Thomas Marshal- Served as Wilson's VP and was Gov of Indiana prior.

Coolidge- Was Harding's VP and was Gov of Massachusetts prior.

Charles Dawes- Coolidge's VP served as US Ambassador to the USSR prior to becoming VP

Henry Wallace- FDR's VP was Sec of Commerce and Agriculture prior

Spiro Agnew- Was Nixon's VP and Gov of MD prior

Nelson Rockefeller- Ford's VP and Gov of NY Prior

GW Bush- Regan's VP and former Director of the CIA