This study explores the enhancement of cupric oxide (CuO) thin films for photovoltaic applications through chromium doping and subsequent annealing. Thin films of CuO were deposited on silicon and glass substrates using reactive magnetron sputtering. Chromium was introduced via ion implantation, and samples were annealed to restore the crystal structure. The optical and structural properties of the films were characterized using X-ray diffraction, spectrophotometry, and spectroscopic ellipsometry. Results indicated that implantation reduced the absorbance and conductivity of the films, while annealing effectively restored these properties. Sample implanted with 10 keV energy and 1 × 1014 cm−2 dose of Cr ions, after annealing had sheet resistance of 1.1 × 106 Ω/sq compared to 1.7 × 106 Ω/sq for non implanted and annealed CuO. Study of crystalline structure confirmed the importance of annealing as it reduced the stress present in the material after deposition and implantation. Density Functional Theory (DFT) calculations were performed to investigate the electronic structure and optical properties of CuO with varying levels of chromium doping. Calculations revealed an energy gap of 1.8 eV for undoped CuO, with significant changes in optical absorption for doped samples. Energy band gap determined using absorbance measurement and Tauc plot method had value of 1.10 eV for as deposited CuO. Samples after implantation and annealing had energy band gap value increased to about 1.20 eV. The study demonstrates that chromium doping and subsequent annealing can enhance the optical and electronic properties of CuO thin films, making them more efficient for photovoltaic applications.