We report on the photoelectrochemical (PEC) splitting of natural water (pH 7) using silicon (Si) nanowires fitted with silver (Ag) dendrites (dendritic nanostructures) as working electrodes (photoanodes). A detailed study of the PEC water splitting process was carried out using linear sweep voltammetry, electrochemical impedance spectroscopy (EIS) and Mott-Schottky (M-S) measurements. The measured photocurrent density of 1.7 mA/cm(2) at an external voltage of -0.6 V under white light illumination demonstrates the efficient decomposition of natural water using dendritic nanostructures as working electrodes. This decomposition is mainly attributed to a significant strengthening of the effective interface between working electrode surface/water and to a decline in the recombination of photoinduced carriers in the presence of Ag dendrites. We propose that the Schottky barrier between Si and Ag dendritic nanostructures favors enhanced photoinduced charge carrier separation. Photoinduced holes in Si are transferred to Ag dendrites (nano branches and leaves) that serve as a charge sink to effectively carry out the PEC oxidation of water. Photoinduced charge carrier separation enhancement was corroborated by the kinetics of our carrier recombination study. We obtained a reasonably long transient period of 80 s for the photoinduced carriers. EIS results show that the charge transfer resistance (150 Omega) of the dendritic nanostructure surface is low enough to promote interfacial charge transfer. This resistance generated a large carrier concentration of similar to 1.1 x 10(20) cm(-3) at the working electrode/water interface according to an M-S analysis. An applied bias-photon-to-current-conversion efficiency level of roughly 4% is reported, demonstrating the efficient PEC splitting of natural water. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.