Defect Polarization‐Metal Anchoring Coupling Enables Ni 2+ /Ti 3+ Dual Active Sites and TiO 6 Octahedral Distortion for Efficient Piezo‐PEC Water Splitting of BaTiO 3

Efficient piezo‐photoelectrochemical (Piezo‐PEC) water splitting is critical for sustainable hydrogen production, yet its performance is largely constrained by sluggish charge separation and inefficient mechanical‐to‐electrical energy conversion. Here, we introduce a defect polarization‐metal anchoring strategy by selectively anchoring Ni at Ba‐vacancy‐rich regions of BaTiO 3 to achieve efficient Piezo‐PEC water splitting. Experimental characterizations and density functional theory (DFT) calculations reveal that Ba vacancies reconstruct the local coordination environment of Ti sites, promoting Ti 3+ formation and TiO 6 octahedral distortion to enhance lattice polarization and the piezoelectric built‐in electric field. Ni anchoring further enhances Ti 3d‐Ni 3d‐O 2p orbital hybridization and Ti─O covalency, forming Ni 2+ /Ti 3+ dual active sites. The enhanced covalency establishes delocalized electron transport pathways to suppress bulk carrier recombination, while the dual active sites accelerate the proton‐coupled electron transfer (PCET) via Ti─O─Ni bridges. The reinforced piezoelectric field synergistically couples with the photogenerated field to promote efficient charge separation. Benefiting from these cooperative effects, the Ni/BTO‐Ba V photoanode delivers a photocurrent density of 2.21 mA cm −2 at 1.23 V RHE under ultrasonic‐light coupling, with a piezoelectric coefficient (d 33 ) of 65.13 pm V −1 . This work establishes a universal guideline for synergistic modulation of defect polarization and metal sites, guiding the rational design of high‐performance photoelectrodes.