A new photochromic ZrO2 precursor solution was prepared using zirconium tetra-n-butoxide, 4-(phenylazo)benzoic acid and ethyleneglycol monomethylether. The density functional theory (DFT) calculation has identified that the structure of the synthesized precursor molecule changed by UV irradiation. The two kinds of thin films were prepared using the photosensitive ZrO2 precursor solution without and with UV irradiation. The surface morphology of thin films changed by UV irradiation. It was found that the surface morphology of thin films is controlled by the difference of precursor structure introduced by UV irradiation.