Regularly shaped, single-crystalline ZnO microrods (MRs) with wurtzite structure were prepared via a wet chemical method. The obtained rods possess average diameter and length of 350 nm and 3.5 µm, respectively. Besides, WO 3 nanorods (NRs) with the size of 20 nm in diameter and 120 nm in length were synthesized by hydrothermal route. A facile solid state reaction route was employed to synthesize the WO 3 /ZnO structure by grinding WO 3 NRs powder and ZnO MRs powder with various weight ratios (1:2, 1:1 and 2:1) together at room temperature without any surfactant and template. WO 3 NRs were sprinkled on ZnO MRs surface and it was observed that the amount of WO 3 significantly affected the overall surface of ZnO MRs. Furthermore, NH 3 gas-sensing property of the obtained products were studied and compared with that of sole ZnO MRs sample. The results demonstrated that the sensors based on WO 3 /ZnO structures possessed larger response, better selectivity, faster response/recovery than the sensor based on pure ZnO MRs. Especially, the gas sensing property of the WO 3 /ZnO composite based sensor with weight ratio of 1:1 was superior to others. However, the operating temperature is quite high (400 C). The mechanism of gas sensing was also studied.