Combining the versatility of the electrospinning technique and the hydrothermal growth of nanostructures enabled the fabrication of TiO₂/ZnO composite nanostructures. XRD, FESEM, TEM and EDX analysis confirmed the growth of ZnO nanosheets with a diameter of about 500 nm on the surface of TiO₂ nanofibers. Gas sensing properties of the sensors fabricated from the as-prepared TiO₂/ZnO, TiO₂ and ZnO were systematically investigated. The TiO₂/ZnO sensor exhibits a response of 15.7 to 100 ppm of ethanol at 280 °C, which is much better than pure TiO₂ and ZnO. The enhanced sensing performance to ethanol is mainly attributed to the formation of heterojunctions between TiO₂ and ZnO, which leads to the interfacial transport of excess carriers.