To address the rapid photogenerated carrier recombination issue that limits the efficiency of photocatalytic applications in semiconductors, this article presents for the first time the application of NiCeO x bimetallic oxides synthesized by the hydrothermal method in photocatalytic hydrogen production. By forming an S‐shaped heterojunction with cadmium sulfide (CdS) nanorods, an internal electric field is simultaneously generated to enhance the efficiency of surface carrier separation. Experimental findings reveal that the hydrogen evolution rate for NiCeO x /CdS achieves 8604.78 μmolg −1 h −1 . This result indicates that the establishment of this unique heterojunction facilitates more effective electron movement from NiCeO x to CdS, leading to accelerated charge separation and transfer processes. Both experiments and theoretical calculations have jointly demonstrated that the composite material enhances the hydrogen production rate through photocatalysis and have also revealed the charge transfer mechanism of the S‐scheme heterojunction. This research provides a promising strategy for utilizing novel bimetallic oxide within the domain of photocatalysis and realizing directed electron migration in photocatalytic hydrogen evolution.