AbstractAmong the various photoanode materials investigated for photoelectrochemical water splitting cells, TiO₂ stands out due to its abundance, stability, and favorable valence band edge for water oxidation. In this study, the importance of introducing and combining oxygen and titanium vacancy point defects in anatase TiO₂ photoanodes to improve their performance is unveiled, achieving a photocurrent density of 0.73 (±0.015) mA cm⁻² at +1.23 V_RHE under 100 mW cm⁻² of simulated sunlight or 26.4 mA cm⁻² at +1.23 V_RHE under 100 mW cm⁻² of 365 nm light. The characterization by X‐ray photoelectron spectroscopy, surface photovoltage, and electron paramagnetic resonance demonstrates that these oxygen and titanium vacancies can have both collective and localized positive effects on the material, leading to a narrowing of the bandgap, an increase in donor density, and an increase in hydroxyl groups on the surface of TiO₂. These result in enhanced light absorption, conductivity, and photovoltage, as well as a more negative flat‐band potential and increase in hole flux to the semiconductor–electrolyte interface. These findings provide valuable insights into the role of point defects in modulating the properties of TiO₂ and have important implications for the development of high‐performance TiO₂‐based devices.