We report on the visible light-driven hydrogen production from splitting of water molecules by nitrogen-doped TiO2 (N-TiO2) with a rice grain-like nanostructure morphology. The N-TiO2 nanostructures are prepared using sol-gel and electrospinning methods followed by post-annealing of the composite nanofibers. The nanostructures are characterized by microscopy and spectroscopy. First order rate constants for the visible light-assisted photocatalysis in the degradation of methylene blue (MB) dye are found to be 0.2 x 10(-3) and 1.8 x 10(-3) min(-1) for TiO2 and N-TiO2 (5 wt% of nitrogen), respectively. The N-TiO2 utilized in water splitting experiments and evaluated hydrogen (H-2) of 28 and 2 mu mol/h for N-TiO2 and TiO2, respectively. The improvement may be attributed due to the N-doping and higher surface area as similar to 70 m(2)/g. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.