Enabling Si photoanodes for efficient solar water oxidation would facilitate the development of solar fuel conversion, but it is challenging owing to Si surface passivation via photo-induced corrosion in aqueous electrolytes. To overcome this challenge, most approaches have focused on improving the stability of Si by coating dense and thin protective layers using high vacuum-based techniques such as atomic layer deposition. However, these procedures are costly, making scalability for practical applications difficult. Herein, we report a modified electroless deposition (ELD) method to uniformly deposit protective and catalytic Ni films on Si wafers, resulting in efficient and stable Si photoanodes for solar water oxidation. The optimized Ni/n-Si photoanode achieves an onset potential of ~ 1.09 V vs. a reversible hydrogen electrode and a saturation current density of ~ 27.5 mA/cm² under AM 1.5 G illumination at pH 14. The ELD method is additionally capable of Ni deposition on a 4-inch n-Si wafer, demonstrating the first 4-inch Si photoanode. The solar water oxidation of the ELD-Ni/n-Si photoanode can be further improved by surface texturing, built-in n–p junctions, or coupling with more efficient catalysts.