Photocatalytic water splitting is a promising approach to converting solar energy into green hydrogen. As an effective photocatalyst, RhxCr2–xO3/SrTiO3has been widely studied for water splitting, mainly synthesized using SrCl2molten salt as the reaction media. This research systematically studied the effect of molten salts and Al doping in order to test and integrate the combinatorial effect of the modifications of SrTiO3-based catalysts. A series of SrTiO3and Al-doped SrTiO3(Al:SrTiO3) were synthesized by the flux method with three molten salts (NaCl, KCl, and SrCl2·6H2O) at different annealing temperatures (900 and 1000 °C). Cocatalyst, RhxCr2–xO3, was loaded on the surface of Al-doped SrTiO3by impregnation and photodeposition methods for comparison. The photocatalytic performance of overall water splitting was evaluated in pure water under UV and AM 1.5G simulated sunlight. A significant improvement in photocatalytic activity was observed in Al-doped RhxCr2–xO3/SrTiO3. Especially Al-doped RhxCr2–xO3/SrTiO3synthesized by KCl molten salt showed the highest hydrogen evolution rate with the synergy effect of molten salt and Al doping. Furthermore, hydrogen evolution rates were further enhanced by loading core–shell RhxCr2–xO3using in situ photodeposition instead of impregnation, reaching 784 and 431 μmol h–1g–1H2under 365 nm UV light and AM 1.5G irradiation, respectively.