Hematite (alpha-Fe2O3) has abundant reserves and an appropriate bandgap of similar to 2.1 eV for H-2 production using water splitting. However, its potential application to solar water splitting is seriously limited by the extremely high charge recombination rate of the charge carriers. The present work investigates the photoelectrochemical (PEC) performance of molybdenum (Mo) doped alpha-Fe2O3 thin-film electrodes. The Mo-doped alpha-Fe2O3 samples were prepared by a hydrothermal method and then loaded with different Mo ratio to optimize the photocurrent density. The morphological characterization and crystal structure identified by FE-SEM, Raman, XRD, XPS and UV-vis analyses. Mo doping of alpha-Fe2O3 , significantly enhanced the photocurrent density. The alpha-Fe2O3 film with optimized Mo-doped amount (10% Mo-doped alpha-Fe2O3) had a photocurrent density of 0.75 and 1.2 mA cm(-2) in front and back-side illumination, respectively at 0.6 V versus Ag/AgCl under 100 mWcm(-2) with an electrolyte of 1 M (pH = 12) aqueous NaOH solution, which are similar to 10 and 17 times higher than that of the pure alpha-Fe2O3 photoanode. The doping of Mo onto pure alpha-Fe2O3 increased the donor concentration 1.3-fold, reduced the width of the space charge layer (W-SCL) 1.2-fold, and decreased the flat band potential (V-fb) 1.6-fold, which improved the photoelectrochemical efficiency.