Pure CdO nanostructured thin films and Ag doped with 1.0, 2.0 and 4.0 wt% doping concentrations were fabricated successfully on glass substrates with a cost-effective spin coating technique. The prepared films exhibit a cubic crystal structure oriented along (111) plane. The surface morphology of the pure CdO films shows a cauliflower shape structure, becomes granular, and compact at high Ag doping concentration. Raman spectra of the films reveal LO (longitudinal optical) and TO (transverse optical) vibration modes at 406.80 cm⁻¹ and 566.54 cm⁻¹. The absorption of the films significantly varies with Ag doping concentrations and as a result, the electronic structure of the films is tailored. Moreover, the optical band gaps vary in the range of 1.42–1.70 eV. In addition, the optical parameters n, k were studied in correlation with Ag doping concentrations. The obtained room temperature photoluminescence spectra of the prepared films show a broad peak at ∼350 nm. The third order nonlinear optical parameters of the films were also examined systematically.