Gas sensing is of significant importance in a wide range of disciplines, including industrial safety and environmental monitoring. In this work, a low-cost SILAR (Successive Ionic Layer Adsorption and Reaction) technique was employed to fabricate pure CuO, Zn-doped CuO, and Na-doped CuO nanotextured films to efficiently detect CO2 gas. The structures, morphologies, chemical composition, and optical properties of all films are characterized using different tools. All films exhibit a crystalline monoclinic phase (tenorite) structure. The average crystallite size of pure CuO was 83.5 nm, whereas the values for CuO/Zn and CuO/Na were 73.15 nm and 63.08 nm, respectively. Subsequently, the gas-sensing capabilities of these films were evaluated for the detection of CO2 in terms of sensor response, selectivity, recovery time, response time, and limits of detection and quantification. The CuO/Na film offered the most pronounced sensitivity towards CO2 gas, as evidenced by a sensor response of 12.8% at room temperature and a low limit of detection (LoD) of 2.36 SCCM. The response of this sensor increased to 64.5% as the operating temperature increased to 150 °C. This study thus revealed a brand-new CuO/Na nanostructured film as a highly effective and economically viable sensor for the detection of CO2.