Molybdenum (Mo)-doped Monoclinic Bismuth Vanadate (Mo-BiVO4; BVO) catalysts were fabricated via a simple dip coating method. We systematically studied the effect of Mo-doping with various concentration (1-5%) in BVO electrode through photoelectrochemical (PEC), Mott-Schottky and impedance measurement. Intermediate heat treatment and number of successive dip coating deposition were utilized to control the monoclinic crystallization and thickness of Mo-BVO photoanodes. Furthermore, the effect of Mo-doping in morphology, structure, chemical states and optical properties of the obtained electrodes were characterized by different physicochemical and morphological methods BVO with 2% Mo doping (2% Mo-BVO) showed the best PEC performance, of about 15 times higher than that of the pure BVO. Improved charge carrier transport and optimized light absorption obtained upon Mo doping into the BVO crystal lattice while the monoclinic scheelite structure with small band-gap was retained. To understand the effect of Mo-doping, Mott-Schottky and Impedance measurement carried out, in order to evaluate the donor concentration and conductivity of pure BVO and Mo-BVO. Interestingly, 2% Mo-BVO showed the maximum donor concentration (5.7E+27) and minimum flat band potential (V-fb=-0.45) compared to other prepared electrodes. Furthermore, we attempt to discuss the improved PEC performance of Mo-BVO using high donor concentration, up-shifting of Fermi level and consequently facilitating electrons transport in Mo-BVO compared to pure BVO.