In this paper, we investigate the morphology, optical, and electrical properties of silicon nanowire (SiNW) arrays and their applications on inorganic/organic hybrid solar cells. The SiNW arrays are obtained by two kinds of metal-assisted chemical etching (MacEtch) processes. One is depositing assisted metal, for example, Ag, by an electron gun evaporator before etching (BE). The other is depositing assisted Ag during the etching (DE) process. The results reveal that BE method MacEtch can produce more uniform and denser SiNW arrays, but the coverage of organic materials to SiNWs is less. In terms of optical properties, the BE method SiNW arrays have higher reflectance than the DE method ones, except the wire length less than 1 µm in the wavelength range less than 500 nm. Regarding the electrical property, the minority-carrier lifetime is higher for the DE method SiNW arrays because of less surface area of SiNWs. Therefore, the best cell performance happens on the DE method SiNW/organic hybrid solar cell with wire length less than 1 µm. The short-circuit current density (Jsc) is 28.55 mA/cm2, open-circuit voltage (Voc) is 0.524 V, and power conversion efficiency (PCE) is 9.56%. Copyright © 2013 John Wiley & Sons, Ltd.