We report the fabrication of one dimensional Silicon nanowires (Si NWs) using p-Si (100) substrate through facile two step metal assisted chemical etching (MACE) approach. The evolution of structural and optical properties of Si NWs by etching Si substrate was studied as a function of hydrogen peroxide (H2O2), a strong oxidation agent. The length of the NWs increased linearly with the H2O2 concentrations and reached maximum of 51 gm for etching of 60 min. The merits of metal free Si NWs as photocathode in the photo electrochemical (PEC) neutral water splitting under the visible light was investigated. The performance of the photocathode highly depends on the morphology of Si nanostructure. A high density and well separated Si NWs fabricated by 0.6 M of H2O2 results in maximum photocurrent density of 6 mA cm(-2) with applied bias photocurrent conversion (ABPE) efficiency of 1.1% under visible light illumination. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.