Thin films of ZnS were grown by metal‐organic chemical vapor deposition (MOCVD) method under atmospheric pressure onto glass substrates. ZnO–ZnS:[Ag, Ga] and ZnO:[Ag, Ga] thin films were prepared by oxidation and Ag, Ga doping of ZnS films at temperatures of 700–775 °C for 0.5–1 h. Crystalline quality and luminescent properties were investigated using X‐ray diffraction (XRD), atomic force microscopy (AFM), and photoluminescence. It is found that the doped films have a polycrystalline structure without preferred orientation and consist of small grains gathered into conglomerates. The shape of photoluminescence (PL) spectra of the films depends strongly on the preparation conditions. The ZnO–ZnS:[Ag, Ga] films exhibited the blue and green emission connected with the presence of silver and oxygen, respectively. The ZnO:[Ag, Ga] films revealed the white emission originated from different defect‐related transitions. The possible origin of radiative centers is discussed (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)