Bi2WO6 is one of the simplest members of the versatile Aurivillius oxide family of materials. As an intriguing model system for Aurivillius oxides, BiVO4 exhibits low water oxidation onset potentials (∼0.5–0.6 VRHE) for driven solar water oxidation. Despite this, Bi2WO6 also produces low photocurrents in comparison to other metal oxides. Due to a lack of in situ studies, the reasons for such poor performance are not understood. In this study, Bi2WO6 photoanodes are synthesized by aerosol-assisted chemical vapor deposition. The charge carrier dynamics of Bi2WO6 are studied in situ under water oxidation conditions, and the rate of both bulk recombination and water oxidation is found to be comparable to other metal oxide photoanodes. However, the rate of electron extraction is at least 10 times slower than the slowest kinetics previously reported in an oxide photoanode. First-principles analysis indicates that the slow electron extraction kinetics are linked to a strong anisotropy in the conduction band. Preferred or epitaxial growth along the conductive axes is a strategy to overcome slow electron transport and low photocurrent densities in layered materials such as Bi2WO6.