We reported for the first time that GaOOH nanorods, which were prepared using a facile chemical precipitation method, may display noticeable photocatalytic activities toward methanol oxidation under light illumination, a significant revelation for demonstrating their use as the anode photocatalyst in the half-cell reaction of direct methanol fuel cells (DMFCs). The GaOOH nanorods were further decorated with Au nanoparticles to endow them with increasingly pronounced charge separation, which conduced to a remarkable enhancement in the photocatalytic performance. Time-resolved photoluminescence spectroscopy was employed to depict the charge transfer event across the interface of GaOOH/Au, from which a correlation between photocatalytic efficiency and interfacial charge dynamics was realized. By incorporating GaOOH nanorods into the traditional Pt-catalyzed half-cell reaction, a 12.7% increase in anodic current generation can be attained under light illumination, demonstrating the promising potential of GaOOH as a practical anode photocatalyst in DFMCs. A further enhancement in methanol oxidation current up to 70.8% can be achieved by employing Au-decorated GaOOH nanorods, which was attributed to the efficient charge carrier transfer rendered by the Au decoration. The current study delivers both fundamental and practical importance as it broadens the scope of electrocatalysts for fuel cells, specifically by introducing a new class of highly efficient photocatalysts for promoting electrochemical reactions.