FTO/ZnO/Ag-x films (where x = 0, 2, 4, 6, 8 wt.% dopant) were made by sol-gel/spin-coating technique and precursor zinc acetate dehydrate at room temperature. The samples were synthesized at 500°C calcination temperature for 2 hours. The optical (E g was determined by UV-visible spectroscopy), structural (crystallite size was obtained by X-Ray Diffraction analysis), and geometrical (surface morphology was confirmed by Field Emission Scanning Electron Microscopy) properties of synthesized samples were characterized. By UV-Vis spectra, it was revealed the transmittance reduction corresponding to the absorbance increase in the visible region indicates the merit interaction of silver with ZnO and the photocatalytic properties of the prepared films. These results were closely associated with the extinction coefficient curves. Moreover, it was demonstrated that decreasing optical band-gap (3.24 eV → 2.92 eV) by increased silver-doping, signifying the emergence of the Localized Surface Plasmon Resonance effect within the visible spectrum. This, in turn, extends the photocatalytic activity. The crystalline structure of the samples was investigated through three analytic methods: Scherrer, Williamson-Hall, and Rietveld. The results confirmed that the prepared samples had a hexagonal wurtzite phase of ZnO and body-centered-cubic Ag that formed continuous layers of polycrystalline mixtures of solids onto single-crystalline FTO substrate. Using the FESEM images and watershed algorithm, the granular structure of films statistically was examined in terms of circularity, roundness, and solidity parameters as well as the Feret’s diameter. The analysis obtained for the parameters above was found to correlate with the XRD pattern. Thus, the introduced structure could be applied in water-splitting H2 production photocatalysis applications.