A new approach to prepare hierarchical and fibrous meso-macroporous N-doped TiO2 is attempted at room temperature without using templates by the addition of titanium isopropoxide droplets to the ammonia solution. The catalysts are thoroughly characterized by physico-chemical and spectroscopic method to explore the structural, electronic and optical properties. The photocatalytic activities of the catalyst were evaluated with hydrogen generation. NTP catalyst calcined at 400 degrees C (NTP-400) exhibited 602.7 mu mol/3 h H-2 generation from 10 vol.% methanol under visible light. The excellent photocatalytic activity for NTP-400 is attributed to the porous networks existing in our system with uniform N dispersion throughout the catalyst. The hierarchical and fibrous structures allow easy channelization of electron as in the case of nanotubes for effective surface charge transfer. Along with macroporosity, nitrogen incorporation and mesoporosity play some important roles for enhanced photoactivities. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.