4 wt% CuO–96 wt% TiO2 granules were prepared by a spray drying process. The microstructure and optical property of CuO–TiO2 granules were studied. The results indicate that copper existed in the form of CuO. The spray dried granules possess spherical geometry and smooth surface with grain size in the range of 40–80 μm. CuO–TiO2 has a relatively smaller Eg value (2.85 eV) than TiO2 (3.17 eV). The photocatalytic property of CuO–TiO2 granules was investigated by degradation of a model pollutant (the azo dye methyl orange) under the irradiation of the xenon lamp equipped with a band pass filter of 365 nm. The CuO–TiO2 spray-dried granules degrade about 10% more MO than TiO2 spray-dried granules under UV irradiation within the same time. The XPS spectra suggested that Cu2+ and reduced copper species were coexistent in reacted CuO–TiO2 photocatalyst. The improvement of photocatalytic activity for CuO–TiO2 was mainly attributed to effective separation of photo-generated electron–hole pairs in the presence of CuO.