The band edge positions of semiconductors determine functionality in solar water splitting. While ligand exchange is known to enable modification of the band structure, its crucial role in water splitting efficiency is not yet fully understood. Here, ligand‐engineered manganese oxide cocatalyst nanoparticles (MnO NPs) on bismuth vanadate (BiVO4) anodes are first demonstrated, and a remarkably enhanced photocurrent density of 6.25 mA cm−2 is achieved. It is close to 85% of the theoretical photocurrent density (≈7.5 mA cm−2) of BiVO4. Improved photoactivity is closely related to the substantial shifts in band edge energies that originate from both the induced dipole at the ligand/MnO interface and the intrinsic dipole of the ligand. Combined spectroscopic analysis and electrochemical study reveal the clear relationship between the surface modification and the band edge positions for water oxidation. The proposed concept has considerable potential to explore new, efficient solar water splitting systems.

The band edge positions of semiconductors determine functionality in solar water splitting. In article number https://doi.org/10.1002/advs.201800727, Ki Tae Nam, Ho Won Jang, and co‐workers demonstrate cascade photoanodes with ligand engineered manganese oxide co‐catalyst nanoparticles to achieve enhanced photoelectrochemical performance. The proposed concept has considerable potential to explore a new efficient solar water splitting system.