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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.