A modified internal gelation process for the preparation of porous zirconia microspheres has been developed. The conventional method has been modified by adding a surfactant in the feed broth. The effects of variation of surfactant concentration, washing techniques and temperature of calcination on the pore volume and the surface area of the microspheres have been studied. The conditions were optimized to obtain porous stable microspheres suitable for various applications. The microspheres were characterized by surface area analysis, pore volume analysis, thermogravimetric analysis and X-ray diffraction. The ion exchange behavior was studied using pH titration. (C) 2008 Elsevier Ltd. All rights reserved.