Perovskite LaFeO3 is regarded as one of the promising photocatalysts for solar splitting of water to hydrogen and oxygen due to its suitable band edge positions, visible light absorbance, and high chemical stability. To further improve its photocatalytic performance of LaFeO3, the effects of solute concentration in the KCl-flux growth and partial A– and B–site substitution are investigated in this work. Controlling the solute concentration in the range of 1–20 mol% is crucial to grow phase-pure LaFeO3 crystals with idiomorphic shape. With increasing the solute concentration, the flux-based growth route gradually changes to a solid state-based growth route because of a decrease in solubility and an increase in the crystallization core number. The La1−xSrxFe1−yTiyO3 (x,y = 0,0; 0,0.15; 0.15,0; 0.1125,0.0375; 0.0375,0.1125; and 0.075,0.075) crystals were also synthesized by a KCl-flux method to explore the effect of partial Sr2+-to-La3+ and/or Ti4+-to-Fe2−4+ substitution on photocatalytic performance of LaFeO3. The Sr2+–Ti4+ co-substitution is found to enhance the photocatalytic performance of LaFeO3 as compared with the corresponding individual substitution (Sr2+ or Ti4+). The highest photocatalytic hydrogen generation rate (83.2 μmol h−1) was observed for Pt-photodeposited La0.925Sr0.075Fe0.925Ti0.075O3 crystals in 5-h reaction due to the improvement of both bulk properties and photoactivity and the reduction in both grain boundaries and lattice defects stemmed from the Sr2+–Ti4+ co-substitution and KCl flux growth. © 2017 Hydrogen Energy Publications LLC