Photocatalytic transfer hydrogenation using water as the proton source has emerged as an attractive and green approach for the catalytic reduction of unsaturated bonds. Herein, we report an oxygen-defective TiO2-supported palladium catalyst (Pd-TiO2-Ov) for efficient photocatalytic water-donating transfer hydrogenation of anethole towards 4-n-propylanisole in a high yield of 99.9%, which is significantly higher compared to the pristine TiO2-supported palladium catalyst (Pd-TiO2, 74%). The enhanced performance is ascribed to the presence of oxygen vacancies, which facilitate light absorption and suppress the recombination of photogenerated electron-hole pairs. Furthermore, the Pd-TiO2-Ov is versatile in hydrogenating various alkene substrates including those with hydroxyl, ether, fluoride, and chloride functional groups in full conversion, thus offering a green method for transfer hydrogenation of alkenes. This study provides new insights and advances in current hydrogenation technology with water as the proton source.