In this work, hollow spherical Pt-loaded WO3/ZnO heterostructured composites were prepared by a chemical liquid phase synthesis method. The morphology, crystal structure and components of the composites were characterized by SEM, TEM, XRD, XPS, etc. The sensing performance for various gases was also tested. Compared with the pristine WO3 (S = 44@225 °C, 50 ppm) gas sensor, the gas sensor that is functionalized with 1 wt% Pt and 0.5 mmol ZnO (1Pt/WZ-2) has a high response of 842-50 ppm at a relatively low temperature of 100 °C for TEA, with a quick response/recovery time of 34/120 s, a lower detection limit of 50 ppb, and good selectivity and moisture resistance. This study provides a highly efficient synthesis method of composite materials for TEA gas detection and the sensitivity mechanism is also discussed in detail.