Multilayer assemblies of silver doped ZnS colloid and polycation were fabricated by a self-assembly technique exploiting electrostatic interaction. UV/Vis spectra showed the uniform deposition process and X-ray photoemission spectroscopy (XPS) confirmed the coexistence of silver. It was found that the emission spectra of the silver doped ZnS colloid red-shifted to 528 nm comparing with undoped ZnS colloid. However, the most important finding was that the luminescence intensity of doped ZnS assembled in films was much stronger than that of undoped ZnS in films and that of doped ZnS in the spin-casting film. The mechanism of the enhancement luminescence was discussed.