Taking a colloidal monolayer floating on the surface of a precursor solution as template, free-standing CdS/Cd composites and pure CdS (CdS-based) ordered porous films had been prepared by a temperature-assisted photochemical strategy. After irradiation with UV-light and heat treatment, the films formed hemi-spherical pores due to the preferable deposition of CdS and Cd onto the PS spheres during the photochemical and interfacial reactions. When the temperature increased from 15 to 60 degrees C, the air/water interface gradually changed into a vapor/water interface on the surface of the solution, resulting in variations of the final compositions. The optical properties of the films were hence changed. Because of the free-standing characteristic, the ordered porous films were first transferred on surface of polluted solutions as photocatalysts, which was a new mode in application of photocatalysts. The photocatalytic activities of films showed regular variations with the compositions in photodegradation of Rhodamine B. This method provides a simple route for tuning the properties of porous films through control of its composition and a flexible application of films on any surface. (C) 2011 Elsevier Inc. All rights reserved.