Due to the large number of industrial applications of transparent conductive oxides (TCOs), this study focuses on one of the most important metal oxides. The RF-magnetron sputtering method was used to fabricate NiO thin films on both quartz and silicon substrates at room temperature under flow of Argon and Oxygen. The sputtered samples were annealed in N2 atmosphere at 400, 500, and 600 °C for 2 hours. Using the AFM micrographs and WSXM 4.0 software, the basic surface parameters, including root mean square roughness, average roughness, kurtosis, skewness, etc., were computed. Advanced surface parameters were obtained by the Shannon entropy through a developed algorithm, and the power spectral density and fractal succolarity were extracted by related methods. Optical properties were studied using a transmittance spectrum to achieve the optical bandgap, absorption coefficient, Urbach energy, and other optical parameters. Photoluminescence properties also showed interesting results in accordance with optical properties. Finally, electrical characterizations and I–V measurements of the NiO/Si heterojunction device demonstrated that it can be used as a good diode device.