A new method for the synthesis of sol−gel films of zirconia-containing nanoparticles of CdS is demonstrated. The method consists of dip-coating of the substrate from a preprepared mother solution containing zirconia tetrapropoxide, cadmium acetate, and ammonium thiocyanate and subsequent annealing of the dried film at elevated temperatures. The films were characterized by optical absorption spectra, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The satellite spectrum of the Cd core levels was analyzed, and thereby the plasmonic structure of the film was resolved. The potential of the process for the fabrication of a class of sol−gel films with semiconductor nanoparticles having optical quality is discussed.