In this work, an atomic-layer Fe₂O₃-modified two-dimensional (2D) porphyrinic metal-organic framework (MOF) was prepared (2D MOF-Fe₂O₃), which exhibits unique interfacial electron-withdrawing effect via charge transfer pathways from Zn₂O₈ and C-O bonds to Fe-O bonds. Concretely, the atomic-layer Fe₂O₃ is deposited on 2D porphyrinic MOF (ZnTCPP) by atomic layer deposition technique to enhance the photocatalytic performance and the subsequent bacteria-killing efficacy. After 20 min light irradiation, the photocatalytic antibacterial efficacy of 2D MOF-Fe₂O₃ can reach up to 99.9%. The underlying mechanism of enhanced photocatalytic activity is that the heterointerface between 2D MOF and Fe₂O₃ can facilitate the transfer of lots of photogenerated electrons from 2D MOF to Fe₂O₃, where 2D MOF and Fe₂O₃ act as electronic donator and receptor, respectively. This work provides an insight into developing highly effective photocatalysts by using electron-withdrawing modulator to optimize charge transfer pathway.