•Mesoporous titania spheres were prepared using CS/PVA hydrogel beads as a template.•The titania spheres prepared was mesoporous structure.•The photocatalytic activity of the mesoporous titania spheres calcined at 500°C was highest. Mesoporous titania spheres were prepared by modified sol–gel method using chitosan/poly(vinyl alcohol) hydrogel beads as a template. Effects of calcination temperature on physical parameters were investigated by X-ray diffraction (XRD), N2 adsorption–desorption, Fourier transform infrared (FT-IR) spectra, thermogravimetry and differential thermal analyses (TG-DTA), high-resolution transmission electron microscope (HRTEM) and scanning electron microscopy (SEM). The photocatalytic activity of mesoporous titania spheres prepared was also evaluated by photocatalytic degradation of phenol as a model molecule under UV irradiation. With increasing calcination temperature, average crystallite size and pore size increased. In contrast, Brunauer–Emmett–Teller (BET) specific surface areas, porosity and pore volumes steadily decreased. Results of characterization proved that prepared titania spheres with highly organized pores were mesoporous structure. The photocatalytic activity of mesoporous titania spheres calcined at 500°C was more effective than those calcined at other temperatures, which were attributed to the porous structure, large BET surface area, crystalline, and smaller crystallite size. This work may provide new insights into the preparation of novel mesoporous titania spheres and further practical applications in the treatment of wastewater.