The wastewater electrolysis cell (WEC) has emerged as a promising decentralized platform for wastewater treatment integrated with hydrogen production. In this study, we developed a heterojunction anode consisting of Ir-doped (5 at%) NiFe2O4 (INFO) spinel as the bottom layer and Sb-doped SnO2 (SS) as the top layer, tailored for chlorine evolution reaction (ClER) in wastewater with near-neutral pH. The INFO/SS heterojunction anode exhibited outstanding ClER activity and selectivity, surpassing the benchmark IrO2 with a current efficiency of 92.1 % at 30 mA cm⁻2 in 50 mM NaCl. Operando X-ray absorption spectroscopy identified Sn-motifs as the active sites for ClER. INFO functioned primarily as an ohmic contact, while inductive charge transfer across the junction enhanced selectivity on the SS. The SS layer also protected the INFO, enabling long-term stability over 300 h in neutral environment. Comparative analysis across heterojunctions led to a design guideline based on grouped electronegativity for selective generation of reactive chlorine species. In real toilet wastewater electrolysis, the INFO/SS anode effectively degraded NH3-N through reactions mediated by reactive chlorine species, and efficiently reduced chemical oxygen demand via Cl• and ClO• radical-mediated oxidation. Hydrogen evolution at the Pt cathode reached 96.1 % current efficiency and 30.1 % energy efficiency. This work marks a significant milestone to expand the practical applications of WEC.​