Abstract: In this study, ZnO–WO3 composite nanorods were synthesized through a combination of hydrothermal growth and sputtering method. The structural analysis results revealed that the as-synthesized composite nanorods had a homogeneous coverage of WO3 crystallite layer. Moreover, the ZnO–WO3 composite nanorods were in a good crystallinity. Further post-annealed the composite nanorods in a hydrogen-containing atmosphere at 400 °C induced the local phase transformation between the ZnO and WO3. The ZnO–WO3 composite nanorods after annealing engendered the coexistence of ZnWO4 and WO3 phase in the shell layer which increased the potential barrier number at the interfacial contact region with ZnO. This further enhanced the ethanol gas-sensing response of the pristine ZnO–WO3 composite nanorods. The experimental results herein demonstrated a proper thermal annealing procedure of the binary composite nanorods is a promising approach to modulate the gas-sensing behavior the binary oxide composite nanorods.