A three-dimensional (3D) multicomponent oxide, Bi2WO6/TiO2 as an example, hierarchical heterostructure was successfully synthesized as a mat via a simple and practical electrospinning-assisted route. The as-prepared hierarchical nanofibrous mal consisted of Bi2WO6 nanoplates growing aslant on the primary TiO2, nanofibers. Interestingly, the nanoplates were further composed of nanoparticles with a size of less than 20 rim. Bi2WO6 With different morphologies and microstructures could be obtained by adjusting the concentration of the precursor, From the mat (10 cm) to the nanoparticle (20 rim), this multicomponent oxide mat due to the self-supporting property Could be layed or hung conveniently anywhere under solar irradiation and recycled easily. Due to the structure-property relationships the 3D Bi2WO6/TiO2 hierarchical heterostructure exhibited enhanced visible photocatalytic activity over that of the bulk Bi2WO6/TiO2 powder (SSR), the Bi2WO6 nanoparticles (BWO), and the TiO2 sample in the decomposition Of both acetaldehyde (CH3CHO) in air and rhodamine B (RhB) in water which are typical model pollutants. Close investigation revealed that the surface area, grain size, and hierarchical heterostructure of the as-prepared Bi2WO6/TiO2 mat could improve the photocatalytic activities.