Cousin to General Stephen Van Rensselaer, Solomon served in the U.S. Army until 1801 when he was named Adjutant General for the New York State Militia. During the War of 1812, Van Rensselaer served as a lieutenant colonel of volunteers. He was wounded during the Battle of Queenston Heights in 1812.
After the war, Van Rensselaer served as a Representative to Congress and as Postmaster of Albany.