WO3 nanoplatelets have been synthesized by electrochemical anodization in acidic electrolytes containing two different complexing agents: fluorides and hydrogen peroxide. The influence of the morphology and size of these nanoplatelets on their photoelectrocatalytic performance has been studied following the degradation of a model organic recalcitrant compound, such as methyl orange (MO). The effect of several supporting electrolytes on this photodegradation process has also been checked. The best MO decoloration was observed for nanoplatelets fabricated in the presence of low H2O2 concentrations, whose distribution and small size made them expose a very high surface area to the problem solution. With this nanostructure, decoloration efficiencies of ca. 100% were obtained after just 60 min. This result is considerably better than others reported in similar works, indicating the excellent behavior of these WO3 nanoplatelets as photoelectrocatalysts.