Martin notched a pair of solo homers and Francisco Lariano turned in a solid seven-inning start that advanced the Pirates to the NL Division Series against division-rival St. Louis Cardinals, which begins Thursday in St. Louis.
Lariano (1-0) held the Reds to one run on four hits and a walk, and struck out five Cincinnati batters.
Pittsburgh, playing in its first playoff game since 1992, got off to a fast start. Marlon Byrd led off the second with a home run and Martin followed one batter later with his first homer of the night to make it 2-0.
Pittsburgh led 3-0 in the top of the fourth when the Reds got on the board with an RBI single by Jay Bruce. The Pirates responded in the bottom of the inning with an RBI double by Neil Walker and a runs-scoring groundout by Byrd.
Sin-soo Choo tacked on the final run of the Reds' season with a solo homer in the eighth.