Reduced graphene oxide and copper oxide multilayer structures were fabricated in a planar configuration by deposition on both ceramic and Si/SiO2 substrates with interdigitated Au electrodes by the spray method. SEM (scanning electron microscopy), TEM (transmission electron microscopy), XRD (X-ray diffraction), and elemental analysis investigations indicated that graphene oxide (GO) was obtained in a form of interconnected flakes consisting of 6–7 graphene layers for GO with the total thickness of ca. 6 nm and 2–3 layers for rGO with the total thickness of 1nm. The lateral size of one flake reached up to 10 micrometers. Copper oxide was obtained by the wet chemical method. The number of sequential layers of the sensing structure was optimized to obtain good sensitivity and acceptable response/recovery times in response to the oxidizing nitrogen dioxide atmosphere. Both semiconductor partners revealed p-type conductivity. Formation of isotype heterojunctions between both semiconductor partners was taken into account and their influence on electrical transport explained. Optimized sensor structures revealed relative sensitivities reaching several tens of percent and acceptable response and recovery times in NO2 concentration ranged from a few to 20 ppm. Possibility of manufacturing sensors working at room temperature was shown, but at the cost of prolonged response/recovery times.