The Cu-based film catalysts with various additive metals have been successfully prepared by the electroless plating on ZnO nanorods/stainless steel substrates. The microstructure features of the Cu-based films are highly porous and composed of plate-type grains. The addition of zirconium, aluminum, and iron into Cu-based film catalyst can improve the activity and the stability of the film catalysts. The catalytic durability of the Cu-based film catalysts has also been improved by addition of Zr, Al, and Fe into Cu-based films. This is attributed to the formation of the stable ZrO2, Al2O 3, and Fe2O3 nanoparticles with good dispersion in the films.