In this work, we investigated the effect of calcination of nanocrystalline commercial titanium dioxide catalyst (P25) on photocatalytic selective hydrogenation of 3-nitrostyrene. TiO2 supports were calcined under air, hydrogen and nitrogen atmosphere at various temperatures around 600 to 900?C for 5 hours. In order to investigate characteristic and catalytic properties of TiO2 after treatment, treated-TiO2 were analyzed by using X-ray diffraction (XRD), N2-physisorption, X-ray photoelectron spectroscopy (XPS), UV-Vis spectroscopy (UV-Vis), photoluminescence spectroscopy (PL), thermogravimetric analysis (TGA), scanning electron microscope (SEM). Photocatalytic hydrogenation performance of treated-TiO2 were tested under UV light irradiation. The 3-nitrostyrene consumption was linearly related to the photoluminescence intensity (PL intensity). TiO2 calcined in air at 700?C exhibited 70% conversion of 3-nitrostyrene along with 100% selectivity to 3-vinylaniline. This probably due to the synergistic effect of high crystallinity along with optimal of anatase and rutile contents, which led to the reduction of electron-hole recombination process as observed from PL results.