Bismuth(III) oxide-carbodiimide (Bi₂O₂NCN) has been recently discovered as a novel mixed-anion semiconductor, which is structurally related to bismuth oxides and oxysulfides. Given the structural versatility of these layered structures, we investigated the unexplored photochemical properties of the target compound for photoelectrochemical (PEC) water oxidation. Although Bi₂O₂NCN does not generate a noticeable photocurrent as a single photoabsorber, the fabrication of heterojunctions with the WO₃ thin film electrode shows an upsurge of current density from 0.9 to 1.1 mA cm^–2 at 1.23 V vs reversible hydrogen electrode (RHE) under 1 sun (AM 1.5G) illumination in phosphate electrolyte (pH 7.0). Mechanistic analysis and structural analysis using powder X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and scanning transmission electron microscopy energy-dispersive X-ray spectroscopy (STEM EDX) indicate that Bi₂O₂NCN transforms during operating conditions in situ to a core–shell structure Bi₂O₂NCN/BiPO₄. When compared to WO₃/BiPO₄, the in situ electrolyte-activated WO₃/Bi₂O₂NCN photoanode shows a higher photocurrent density due to superior charge separation across the oxide/oxide-carbodiimide interface layer. Changing the electrolyte from phosphate to sulfate results in a lower photocurrent and shows that the electrolyte determines the surface chemistry and mediates the PEC activity of the metal oxide-carbodiimide. A similar trend could be observed for CuWO₄ thin film photoanodes. These results show the potential of metal oxide-carbodiimides as relatively novel representatives of mixed-anion compounds and shed light on the importance of the control over the surface chemistry to enable the in situ activation.