This paper introduced the topology of five-level neutral point clamped (NPC) H-Bridge inverter and its operating principle, and proposed a new algorithm of space vector pulse width modulation (SVPWM), which can be applied to the five-level inverter. In this algorithm, the reference voltage position is located by twelve judging rules, and in order to avoid the abrupt change of output voltage vectors during the process of desired vector changing from one section to another, the method that made the output vector changes of the two adjacent triangles in the opposite direction is used. In this paper, the implementation approaches and concrete steps for the algorithm used to control the five-level inverter were studied with simulation. The simulation results have shown that the proposed algorithm is correct and effective, the harmonics of inverter output voltage are significantly reduced and the amplitude of fundamental voltage also increase significantly, compared with the traditional SPWM method.