The photoelectrocatalytic (PEC) degradation of a persistent and toxic herbicide, atrazine, has been investigated by using a novel and high-performance WO3 nanostructure in the form of nanosheets/nanorods as photoanode. The nanostructure has been synthesized by anodization in acidic media in the presence of a very small amount (0.05 M) of H2O2, and its morphology, as well as its electrochemical and photoelectrochemical properties have been characterized. Atrazine was completely degraded after similar to 180 min of reaction following pseudo-first order kinetics, and 2-hydroxyatrazine was identified as the main intermediate species. Moreover, the s-triazine ring in cyanuric acid (the final intermediate of atrazine degradation and very stable) was partially broken according to the obtained results, indicating the excellent PEC behavior of this WO3 nanostructure.