Abstract Constructing heterojunctions between two semiconductors with matched band structure is an effective strategy to acquire high‐efficiency photocatalysts. The S‐scheme heterojunction system has shown great potential in facilitating separation and transfer of photogenerated carriers, as well as acquiring strong photoredox ability. Herein, a 0D/2D S‐Scheme heterojunction material involving CeO 2 quantum dots and polymeric carbon nitride (CeO 2 /PCN) is designed and constructed by in situ wet chemistry with subsequent heat treatment. This S‐scheme heterojunction material shows high‐efficiency photocatalytic sterilization rate (88.1 %) towards Staphylococcus aureus (S. aureus) under visible‐light irradiation ( λ ≥420 nm), which is 2.7 and 8.2 times that of pure CeO 2 (32.2 %) and PCN (10.7 %), respectively. Strong evidence of S‐scheme charge transfer path is verified by theoretical calculations, in situ irradiated X‐ray photoelectron spectroscopy, and electron paramagnetic resonance.