By creating a p-n heterojunction of molybdenum sulfide (MoSx)/Ti-doped Fe2O3 (Ti-Fe2O3), we successfully addressed electron-hole transfer problems of hematite and thus achieved the enhanced photoelectrochemical (PEC) performance. MoSx/Ti-Fe2O3 with a thin MoSx layer on the surface of Ti-Fe2O3 fabricated a p-n junction that provided facile charge transfer pathways due to an internal electric field between Ti-Fe2O3 and MoSx, and achieved suppressed charge recombination. The optimized MoSx/Ti-Fe2O3 sample showed a 240% increased photocurrent density (3.03 mA cm-2) over pristine Fe2O3 at RHE 1.50 V. All our data including IPCE, PL, and EIS clearly confirmed the improved PEC performance of MoSx/Ti-Fe2O3 achieved by the formation of a p-n junction with a facile electron-hole transport pathway. © The Royal Society of Chemistry.