David Berardan

Introducing ferroelectric polarization has shown great potential to facilitate interfacial charge separation in photoelectrochemical (PEC) water splitting. However, unambiguous evidence of the actual influence of spontaneous ferroelectric polarization, as compared to heterojunction formation, on electron extraction and PEC water splitting is still lacking to date. Herein, core‐shell BaTiO3/TiO 2 nanostructures are designed as photoanodes based on paraelectric cubic and ferroelectric tetragonal phases BaTiO 3 (BTO) perovskite. The cubic and tetragonal crystalline phases are stabilized using selected elaboration methods. Compared to the paraelectric cubic ( c ‐BTO), the ferroelectric tetragonal ( t ‐BTO) leads to a favorable ferroelectric polarization, enhancing directional charge separation and as a consequence to increased photocurrent up to a factor of 1.95. More interestingly, the charge separation efficiency can be tuned by applying positive or negative polarization, with the highest charge separation obtained for the positive one. When loading Ni(OH) 2 as a cocatalyst on the t ‐BTO@TiO 2 photoanode, the Ni(OH) 2 /TiO 2 / t ‐BTO exhibits a high performance and superior stability toward PEC water oxidation with a photocurrent almost 6.7 times that of the reference SiO 2 @TiO 2 . The proposed facilitation may open an avenue to engineer charge separation and transport for high‐performance PEC water oxidation.