Vertically aligned silicon nanowires have been synthesized by the chemical etching of silicon wafers. The influence of a hydrogenated amorphous silicon (a-Si:H) layer (shell) on top of a silicon nanowire (SiNW) solar cell has been investigated. The optical properties of a-Si:H/SiNWs and SiNWs are examined in terms of optical reflection and absorption properties. In the presence of the a-Si:H shell, 5.2% reflection ratio in the spectral range (250 to 1,000 nm) is achieved with a superior absorption property with an average over 87% of the incident light. In addition, the characteristics of the solar cell have been significantly improved, which exhibits higher open-circuit voltage, short-circuit current, and efficiency by more than 15%, 12%, and 37%, respectively, compared with planar SiNW solar cells. Based on the current-voltage measurements and morphology results, we show that the a-Si:H shell can passivate the defects generated by wet etching processes.