Al/TiO2 composite film was successfully deposited on polyester fabrics by using magnetron sputtering techniques. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) were used to examine the deposited films on the fabrics, and the structural colors and anti-ultraviolet property of fabrics were also analyzed. The results indicated that polyester fabrics coated with Al/TiO2 composite films achieved structural colors. The reactive sputtering times of TiO2 films in Al/TiO2 composite films were 10 min, 12 min, 18 min, 20 min, 26 min, 27 min, 30 min and 45 min, respectively, the colors of corresponding fabrics were bluish violet, blue, cyan, green, yellow, yellowish red, orange and blue-green, which was consistent with the principle of the thin film interference. The structure of the TiO2 film in Al/TiO2 composite films was non-crystalline, though the fabrics were heated and maintained at the temperature of 200 °C. The anti-ultraviolet property of the fabrics deposited with Al/TiO2 composite films were excellent because of the effect of Al/TiO2 composite films.