The p-n junction is the principal mode of optoelectronic semiconductor material. At present, we submit a solution-based attempt at the synthesis of nanostructured p-type CuO and n-type ZnO nanocomposite (NC) heterostructure films. Bare and Cobalt (Co)-doped CuO–ZnO NC films have been produced on glass slides using the SILAR (Successive Ionic Layer Adsorption and Reaction) method. The influence of Co-doping concentration on the physical characteristics of CuO–ZnO NC heterostructure films was investigated. XRD spectrums indicated the phase and structural purity of solution-based synthesized CuO–ZnO NC samples. The surface topographical, as well as optical and electrical properties of heterostructure films were, also investigated. While the bare CuO–ZnO NC film has a ∼38% transmission near 1000 nm wavelength region, the 2.0% Co-doped CuO–ZnO NC film has ∼31% of optical transmission. The sheet resistance value of the grown 2.0% Co:CuO–ZnO NC sample is almost 13 times lower than that of the bare CuO–ZnO NC sample at 400 K temperature. As a consequence, our attempt ensures a novel strategy for the production and performance optimization of CuO–ZnO NC heterostructures in the implementation of optoelectronics.