Wastewater electrolysis cells (WECs) for decentralized wastewater treatment/reuse coupled with H2 production can reduce the carbon footprint associated with transportation of water, waste, and energy carrier. This study reports Ir-doped NiFe2O4 (NFI, ~ 5 at% Ir) spinel layer with TiO2 overlayer (NFI/TiO2), as a scalable heterojunction anode for direct electrolysis of wastewater with circumneutral pH in a single-compartment cell. In dilute (0.1 M) NaCl solutions, the NFI/TiO2 marks superior activity and selectivity for chlorine evolution reaction, outperforming the benchmark IrO2. Robust operation in near-neutral pH was confirmed. Electroanalyses including operando X-ray absorption spectroscopy unveiled crucial roles of TiO2 which serves both as the primary site for Cl⁻ chemisorption and a protective layer for NFI as an ohmic contact. Galvanostatic electrolysis of NH4⁺-laden synthetic wastewater demonstrated that NFI/TiO2 not only achieves quasi-stoichiometric NH4⁺-to-N2 conversion, but also enhances H2 generation efficiency with minimal competing reactions such as reduction of dissolved oxygen and reactive chlorine. The scaled-up WEC with NFI/TiO2 was demonstrated for electrolysis of toilet wastewater.​