Herein, we report a 'double-use' strategy to modify BiVO4 photoanodes using CoPOM simultaneously as both a doping agent and a co-catalyst in BiVO4 photoanodes. We show that the combination of both modification routes results in significantly increased photocurrent densities compared with pristine (non-modified) BiVO4, and discuss in detail the mechanistic aspects of the improved activity and stability. These results establish the 'Double-Use' strategy involving CoPOMs as a facile and scalable approach for the development of photoanodes for PEC water splitting.