The emerging polyoxometalate (POM) nanomaterials are transition metal oxygen anion clusters with d0 electronic configurations, which could be attractive and potential photocatalysts. Hence, a nickel (Ni)-substituted polyoxometalate K6Na4[Ni4(H2O)2(PW9O34)2]·32H2O (Ni4POM)-incorporating step (S)-scheme heterojunction was developed to promote photocatalytic activity and stability in H2 and H2O2 production. The multielectron transfer through variable valence metal centers in Ni4POM would facilitate the recombination of invalid charges through the S-scheme pathway. Moreover, incorporating Ni4POM into the S-scheme heterojunction can broaden the light absorption range and meanwhile lead to resistance to photocorrosion to promote the optical and chemical stability of Cd0.5Zn0.5S (CZS). The optimized CZSNi-70 exhibited a H2 evolution rate of 42.32 mmol g–1 h–1 under visible-light irradiation with an apparent quantum yield of 32.27% at 420 nm and a H2O2 production rate of 295.4 μmol L–1 h–1 under 420 nm light-emitting diode irradiation. This work can provide a new view for the development of transition metal-substituted POM-based stable and efficient S-scheme photocatalysts.