It has been reported that photogenerated electrons and holes can be directed toward specific crystal facets of a semiconductor particle, which is believed to arise from the differences in their surface electronic structures, suggesting that different facets can act as either photoreduction or photo-oxidation sites. This study examines the propensity for this effect to occur in faceted, plate-like bismuth molybdate (Bi2MoO6), which is a useful photocatalyst for water oxidation. Photoexcited electrons and holes are shown to be spatially separated toward the {100} and {001}/{010} facets of Bi2MoO6, respectively, by facet-dependent photodeposition of noble metals (Pt, Au, and Ag) and metal oxides (PbO2, MnO x, and CoO x). Theoretical calculations revealed that differences in energy levels between the conduction bands and valence bands of the {100} and {001}/{010} facets can contribute to electrons and holes being drawn to different surfaces of the plate-like Bi2MoO6. Utilizing this knowledge, the photo-oxidative capability of Bi2MoO6 was improved by adding an efficient water oxidation co-catalyst, CoO x, to the system, whereby the extent of enhancement was shown to be governed by the co-catalyst location. A greater oxygen evolution occurred when CoO x was selectively deposited on the hole-rich {001}/{010} facets of Bi2MoO6 compared to when CoO x was randomly located across all of the facets. The elevated performance exhibited for the selectively loaded CoO x/Bi2MoO6 was ascribed to the greater opportunity for hole trapping by the co-catalyst being accentuated over other potentially detrimental effects, such as the co-catalyst acting as a recombination medium and/or covering reactive sites. The results indicate that harnessing the synergy between the spatial charge separation and the co-catalyst location on the appropriate facets of plate-like Bi2MoO6 can promote its photocatalytic activity.