Nanomaterials with unusual architectures or morphologies often exhibit novel functional properties. Here, we apply a simple two-step solution method to synthesize the ZnO/SnO2 microspheres with an average size of 1–2μm, which exhibit a unique core–shell architecture with a uniform dispersion of SnO2 nanoparticles on surfaces of spherical ZnO cores. We further investigate in detail the morphology evolution with reaction time, based upon which a likely growth mechanism is proposed. In property, the prepared core–shell structural ZnO/SnO2 microspheres show excellent gas-sensing functions to ethanol gas of 50ppm at an optimal temperature as low as 250°C, rendering the hybrid microspheres a promising gas-sensing material for the on-site detection of ethanol.