Hierarchical and heterogeneous CuO/NiO nanowall arrays were in situ grown on ceramic tubes via a facile template-free hydrothermal route, and then were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen adsorption-desorption techniques. The resultant composites exhibit network-like CuO/NiO array structures constructed by interconnected porous nanosheets, in which the decoration of CuO nanoparticles in NiO nanowall arrays was confirmed by XRD, XPS and TEM analyses. The 2.84 at % CuO decorated NiO sensor exhibits excellent sensing properties at 133 °C. The response to 5 ppm HS attains 36.9, which increases as high as 5.6 times compared to the NiO one. The detection limit to HS is further decreased from 1 ppb for the pure NiO sensor to 0.5 ppb. The CuO/NiO sensor shows a wide linear range from 50 to 1000 ppb, good repeatability, selectivity and long-term stability, which is expected to be a candidate for ppb-level HS detection in real and complex environment of industrial production. Furthermore, the dominant HS sensing mechanism is discussed from the view of the homo- and hierarchical architecture of the CuO/NiO arrays as well as the chemical and electronic sensitization effects of CuO decoration.