In this experimental studies, we report the synthesis of TiO2 co-doped by both cationic and anionic sites by simple sol-gel based method. All the prepared samples exhibit the anatase crystalline morphology however, showed lattice distortion caused by the displacement of Ti4+ sites by Gd3+. The improved visible absorption is witnessed by the Gd and N co-doping with an assured redshift in the absorption edge. The N and Gd displacement inside TiO2 lattice accompanied by the creation of O-Ti-N and Gd-O-Ti bonds are characterized by the X-ray photoelectron spectra. The strong resonance signal by Gd4f electrons in the electron paramagnetic resonance spectroscopy further substantiate the displacement of lattice cites of TiO2 by Gd3+ ions. The longevity of the photo produced charges observed in fluorescence spectra of Gd and N co-doped TiO2 is because of the effective transfer of charges to the defect sites. The aforementioned catalysts are tested for their capacity for the H-2 production from water splitting. The 2 wt% gadolinium and nitrogen co-doped TiO2 has shown 10764 mu mol g(-1) H-2 production which is 26 times higher than the commercial Degussa P-25 catalyst. The enhanced activity for hydrogen production can be attributed to factors such as increased absorptivity under visible light and effective charge carrier separation. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.