The electrocatalytic activity of tin doped TiO(2) hollow sphere particles has been examined in acid solution. Titania hollow spheres have been synthesized by using poly(styrene-methacrylic acid) latex particles as a template, and tin was doped over spheres with the appropriate amount of SnCl(2)center dot 2H(2)O solution in HCl. The surface characteristics have been evaluated by XRD, SEM and TEM analysis, XRD analysis has shown the presence of rutile SnO(2) and TiO(2) phase in the catalysts; and the peak intensity for SnO(2) phase increased with rise in the calcination temperature indicating the critical growth of tin on the surface of the catalysts. Diameter of pure TiO(2) hollow spheres and Sn doped samples were found from SEM and TEM images in the range of 1-1.2 and 0.4-0.6 mu m, respectively. TGA has been performed with the uncalcined 40 wt% Sn doped TiO(2) catalyst. The peaks for hydrogen and oxygen production are present significantly for all the hollow sphere samples in cyclic voltammograms; but peaks for hydrogen production is more prominent in 20 and 40 wt% Sn/TiO(2) catalysts, The performances of the hollow sphere electrocatalysts were evaluated up to current densities of SO mA cm(-2) during anodic polarization measurement. Sn/TiO(2) electrocatalysts have also shown long time electrochemical stability in acidic media. (C) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.