Sluggish charge kinetics in photocatalysts and slow hole transfer in oxidation half-reaction severely limit the photocatalytic activity of hydrogen evolution. ZnIn 2 S 4 with an asymmetrical layered structure of [S-In]-[S-In-S]-[Zn-S] unit cell is a promising material offering asymmetrical crystal polarization to overcome the limitation; however, the polarization-induced internal electric field by this material remains largely unexplored. Herein, the polarization-induced internal electric field of ZnIn 2 S 4 by engineering the polarity intensity in microscopic units is demonstrated for the first time. Specifically, ultrathin ZnIn 2 S 4 nanosheets are employed to establish a Ni 12 P 5 /ZnIn 2 S 4 -O (NP/ZIS-O) system with powerful bulk and interface cascade electric field by the oxygen doping and ohmic junction. Enabled by such a design, the photogenerated electrons can rapidly migrate to NP active sites, suppressing the photogenerated electron-hole pair recombination on ZIS-O. To further overcome the inefficient hole transfer in oxidation half-reaction, the preferential dehydrogenation of the α-CH bond in benzyl alcohol is utilized as a vehicle to facilitate hole transfer.As a result, a remarkably enhanced H 2 generation of 15.79 mmol g -1 h -1 is achieved on NP/ZIS-O, which is 8.16-fold higher than that of pristine ZnIn 2 S 4 . Meanwhile, as a value-added oxidation product, benzaldehyde can be produced at the rate of 17.63 mmol g -1 h -1 . This work presents a collaborative strategy for engineering charge behavior in photocatalysts with polarization features, and provides insights into materials design toward photocatalytic hydrogen production and organic synthesis from the angle of charge kinetics.