In this study highly oriented, rutile phase one dimensional Titania nanorod array (TiO2 NRA) modified by gadolinium doping were synthesized on the conductive glass substrate (FTO) by the hydrothermal method. The effect of Gd doping on the photoelectrochemical performance of TiO2 NRA was investigated. Crystal phase, structural, morphological and composition characteristics of these synthesized photoelectrodes were analyzed by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), and atomic force microscopy (AFM). FE-SEM images clearly show that some of the Gd dopant is uniformly distributed on the surface of TiO2 NRA in the form Gadolinia (Gd2O3) microsphere. These gadolinia microsphere play an important role in reducing the surface recombination of electron and hole supported by photoluminescence's studies. Linear sweep voltammetry results show that Gd doping results in a two-fold increase in photocurrent density as compared to pristine TiO2 NRA. UV visible spectra, and Mott-Schotty measurements show that Gd doping shift the flat-band potential of TiO2 NRA more toward negative potential that results in effective charge separation and transportation in the Gd doped TiO2 NRA (Gd@TiO2 NRA). Applied biased photon to current efficiency (ABPE) equation was used to find solar to hydrogen efficiency (STH). Gd@TiO2 NRA show optimum conversion efficiency of similar to 0.64% at 0.03 V vs Ag/AgCl, while pristine TiO2 NRA display similar to 0.33% at -0.21 V vs Ag/AgCl. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.