Photocatalytic water splitting into hydrogen production provides a new avenue to produce clean chemical fuels. However, developing high‐efficiency photocatalytic materials still remains a challenge till now. Herein, multiobjective‐optimization MoS 2 /Cd‐ZnIn 2 S 4 /CdS (MS/CZIS/CS) composites are successfully constructed by an in situ structure‐tailored technique. Benefiting from the synergistic feature integrating sulfur vacancy, II‐type CZIS/CS heterojunction and Schottky‐type MS/CS heterojunction, such composites not only effectively steer photogenerated carrier transfer but also markedly expedite surface reaction kinetics for hydrogen reduction reaction. As a result, an optimal hydrogen evolution rate of 11.49 mmol g −1 h −1 is achieved over the MS/CZIS/CS catalysts, which is approximately 4.79 times higher than that of pristine ZIS (2.40 mmol g −1 h −1 ). This work provides some new inspirations for the steering of carrier transfer and the design of multiobjective‐optimization photocatalysts with high efficiency.