Fenton technology has garnered significant attention for the deep removal of low-concentration emerging contaminants due to its remarkable oxidation performance. However, the traditional mineralization process for emerging contaminants requires a substantial amount of hydroxyl radicals (HO˙), leading to excessive consumption of H₂O₂. Through interfacial engineering of Fe–Zr bimetallic catalysts (FeZrO_x), this study demonstrates synergistic enhancement of phenolic pollutant removal at heterojunction interfaces while achieving an 80% reduction in H₂O₂ dosage compared to traditional Fe₂O₃ systems. The chemical states of Fe and Zr at the (104)/(111) heterojunction interface in FeZrO_x exhibit marked modifications relative to their monometallic Fe₂O₃ and ZrO₂ counterparts. The elevated charge density at interfacial Fe sites in FeZrO_x promotes HO˙ generation, while optimized antibonding orbital composition below the Fermi level in bisphenol A adsorbed on Zr sites enhances hydrogen abstraction and subsequent polymerization. This Fe–Zr synergy at the (104)/(111) heterojunction concurrently suppresses HO˙ diffusion losses and directs phenolic pollutant (e.g., phenol and bisphenol A) polymerization within the reactive interface, thereby reducing H₂O₂ consumption compared to monometallic systems.