Bi2WO6 flower-like materials (FMs) were prepared by hydrothermal method and reduced by in situ reduction reaction to obtain Au@Bi2WO6 FMs. The samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS). It is found that the calculated OV content of Au@Bi2WO6 FMs is 25.16% whereas that of Bi2WO6 FMs is 20.81%, which provided potential active sites for gas adsorption and then enhanced excellent sensing property. In addition, the performance of Au@Bi2WO6 FMs sensors was evaluated by detecting volatile and toxic gases such as formaldehyde, methanol, acetone, benzene, toluene, and xylene. It revealed that the optimal operating temperatures for the Bi2WO6 FMs and Au@Bi2WO6 FMs sensors were 290°C and 260°C, respectively. Compared Au@ Bi2WO6 FMs sensor and Bi2WO6 FMs one, the best response of the front was 250 (900) to 100 (800) ppm formaldehyde whereas that of the latter was 90 (230). Therefore, Au@ Bi2WO6 FMs have good response and selectivity, which are promising candidates for formaldehyde detection.