Novel template-free millimetre-size TiO2 photocatalyst spheres with a considerable degree of consistency in their shape and size were developed using sol-gel route. The photocatalyst was prepared by developing a bond between the pre-calcined TiO2 particles in suspension of TiO2 nanoparticles (composite sol-gel) formed by the assistance of a polymeric compound structure. Synthesis variables such as reactant concentrations. pH, drying process and calcination temperature were studied in order to improve the attrition resistance, while maintaining the photoefficiency of the catalyst. X-ray diffraction (XRD), scanning electron microscope (SEM), BET specific surface area and thermo gravimetric analyses (TGA) were used to characterize the photocatalyst. The photocatalytic activities of this mechanically robust photocatalyst was assessed in a laboratory scale fluidized bed photocatalytic reactor using UV irradiation at 254 nm and formic acid (FA) as a model organic compound. (C) 2011 Elsevier B.V. All rights reserved.