Large-scale novel core–shell structural SnO₂/ZnSnO₃microspheres were successfully synthesized by a simple hydrothermal method with the help of the surfactant poly(vinyl pyrrolidone) PVP. The as-synthesized samples were characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy（HRTEM).TheresultsindicatethattheshellwasformedbysinglecrystallineZnSnO₃nanorods and the core was formed by aggregated SnO₂nanoparticles. The effects of PVP and hydrothermal time on the morphology ofSnO₂/ZnSnO₃were investigated. A possible formation mechanism of these hierarchi-cal structures was discussed. Moreover, the sensor performance of the prepared core–shellSnO₂/ZnSnO₃nanostructures to ethanol was studied. The results indicate that the as-synthesized samples exhibited high response and quick response-recovery to ethanol.