A photo-sensitive composite film is disclosed, which includes plural metal nano-particles and a porous anodized aluminum oxide film. The nanoparticles can be hollow or solid with unrestricted shapes of varying diameters and lengths. The plural metal nanoparticles are completely contained in holes and attached to the bottom of the holes of the anodized aluminum oxide film, and the electrical conductivity of the photo-sensitive anodized aluminum oxide film can be changed by light exposure on the metal nanoparticles from surfaces of the anodized aluminum oxide film. The structure of the photo-sensitive anodized aluminum oxide film of the present invention is uncomplicated and the manufacturing steps thereof are simple, and therefore the photo-sensitive anodized aluminum oxide film of the present invention is of great commercial value. Also, a method of manufacturing the above photo-sensitive composite film and a photo-switched device including the same are disclosed.