The treatment of wastewater that includes toxic organic pollutants such as dyes, phenoaniline, phenols and their derivatives is still a challenge due to their biorecalcitrant and acute toxicity to the widespread acceptance of water recycling. Three-dimensional (3D) Bi2WO6 microsphere was synthesized by the hydrothermal method using Bi(NO3)3 and Na2WO4 as raw materials. This structure exhibits high photocatalytic activity for the dyes, toxic organic compounds. The degradation of methlyene blue is 100% in 30 min, 4-nitrylphenol is 95% in 60 min and p-nitrylphenol is 95% in 75 min in ultraviolet (UV) light irradiation. 3D Bi2WO6 microsphere is also a good photocatalyst to treat the printing and dyeing sewage, and exhibits high repeatability. After being used the 20th time, Bi2WO6 still has high activity to degrade the printing and dyeing sewage, which is very important for a photocatalyst to be used in industry. This study will pave a new way to treat industry wastewater.