We present the rectifying and nitrogen monoxide (NO) gas sensing properties of an oxide semiconductor heterostructure composed of n-type zinc oxide (ZnO) and p-type copper oxide thin layers. A CuO thin layer was first formed on an indium-tin-oxide-coated glass substrate by sol-gel spin coating method using copper acetate monohydrate and diethanolamine as precursors; then, to form a p-n oxide heterostructure, a ZnO thin layer was spin-coated on the CuO layer using copper zinc dihydrate and diethanolamine. The crystalline structures and microstructures of the heterojunction materials were examined using X-ray diffraction and scanning electron microscopy. The observed current-voltage characteristics of the p-n oxide heterostructure showed a non-linear diode-like rectifying behavior at various temperatures ranging from room temperature to 200 ℃. When the spin-coated ZnO/CuO heterojunction was exposed to the acceptor gas NO in dry air, a significant increase in the forward diode current of the p-n junction was observed. It was found that the NO gas response of the ZnO/CuO heterostructure exhibited a maximum value at an operating temperature as low as 100 ℃ and increased gradually with increasing of the NO gas concentration up to 30 ppm. The experimental results indicate that the spin-coated ZnO/CuO heterojunction structure has significant potential applications for gas sensors and other oxide electronics.