In this study, CdS/ZnO (2:3 mol%) thin films are successfully deposited on quartz substrates by using the sputtering technique. Good images on the structural and optical characteristic features of CdS/ZnO thin films before and after annealing are obtained. The CdS/ZnO thin films are annealed respectively at temperatures of 373 K, 473 K, and 573 K and the structural features are examined by XRD, ATR-FTIR, and FESEM. The optical properties of CdS/ZnO thin films such as refractive indices, absorption coefficients, optical band gap energy values, Urbach energy values, lattice dielectric constants, and high frequency dielectric constants are determined from spectrophotometer data recorded over the spectral range of 300 nm–2500 nm. Dispersion parameters are investigated by using a single-oscillator model. Photoluminescence spectra of CdS/ZnO thin films show an overall decrease in their intensity peaks after annealing. The third-order nonlinear optical parameter, and nonlinear refractive index are also estimated.