MWCNT-TiO2 hybrid nanostructures are prepared using sol-gel and electrospinning followed by post annealing of as-spun nanofibers at 450 degrees C per 1 h in air. These hybrid nanostructures composed of MWCNTs varied from 0 to 20% (w/w) and are characterized by SEM, TEM, XRD, and FT-IR analysis. MWCNT-TiO2 hybrid structures are utilized in commercially available Methylene blue (MB) dye degradation and found that 2% of MWCNT exhibit superior kinetic constant 6.379 x 10(-3) min(-1) extracted. In addition, we demonstrate that the doping of MWCTs within TiO2 leads to a significant enhancement of the UV-vis light assisted photocatalytic activity is optimized in comparison with higher (5, 10 and 20%) compositions. UV-vis assisted photocatalytic hydrogen is evolved by photoelectrolytic splitting of water by using MWCNT-TiO2 hybrid nanostructures as electrode. Copyright (c) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.