The addition of a metal complex and an additive to a polymer supported on a reflective surface, which was then exposed to monochromatic ultraviolet (UV) light, resulted in well-ordered metal nanoparticles. Their row spacing is similar to the distance between the constructive interference regions. This could occur even in glassy polymers. Transmission electron microscopy, absorption spectroscopy and dynamic secondary ion mass spectrometry in conjunction with molecular dynamics simulation all revealed how and why the metal ions and/or ion clusters were transported in the glassy polymer films. Furthermore, the diffusion coefficient of the metal ions and/or ion clusters in the film, probably in the shape of ion clusters, was discussed. Our results showed novel criteria to design and construct multi-layered polymer and metal composite films using a simple, inexpensive method.