The silicon/poly(3, 4-ethylenedioxythiophene) core/shell organic/inorganic nanowire array (SiNWs/PEDOT) hybrid heterojunction solar cells are successfully fabricated by silver-assisted chemical etching method and vapor phase polymerization processes. The SiNWs/PEDOT hybrid solar cell shows that the performance is improved greatly and an excellent power conversion efficiency of 3.23% is achieved, which is as seven times as large as that of the planar cell without the nanowire structure. In addition, the studies of the reflectance, the I-V curve and the external quantum efficiency show that the great enhancement of performance for the SiNWs/PEDOT cell is due to the fact that the Si/PEDOT core/shell nanowire structure is successfully fabricated by vapor phase polymerization method, resulting in a high light trapping effect, a large junction area and an enhancement of the carrier collection efficiency.