A series of Al-doped BiVO4 composites have been synthesized via the hydrothermal method for methylene blue (MB) degradation application. The reasons for the improvement of photocatalytic performance was explained from the perspective of optics. Transient photovoltage (TPV) measurements suggested that the surface states have the priority to capture photogenerated carriers, and the Al2O3 surface passivation layer can prolong the lifetime of charge carrier. The results of surface photovoltage (SPV), transient photovoltage (TPV), and surface photocurrent (SPC) measurements suggested that the coexistence of Al3+ and Al2O3 caused by the appropriate doping would improve the transfer property and prolong the lifetime of photogenerated carriers. Finally, the possible photocatalytic mechanism is expounded to illustrate the photogenerated charge behavior under visible light irradiation. This work provides a better understanding of the synergistic effect of Al-doping and Al2O3 passivation layer on enhancing the photocatalytic performance.