This study presents a highly selective electrochemical urea oxidation reaction (UOR) with efficient hydrogen evolution, achieved through atomically isolated asymmetric Ni–O–Ti sites on a Ti foam anode. These sites exhibit a 99% nitrogen selectivity for urea oxidation, surpassing previously reported Ni-based electrocatalysts with selectivities below 55%. The asymmetric sites, featuring oxygenophilic Ti adjacent to Ni, favor interaction with the carbonyl group in urea, preventing premature C=N bond breakage and enabling selective intramolecular N–N coupling to N₂. The system also delivers a hydrogen evolution rate of 22.0 mL h⁻¹ when coupled to a Pt cathode under 213 mA cm⁻² at 1.40 V_RHE. A prototype device powered by a commercial Si photovoltaic cell is developed for solar-powered on-site urine processing and decentralized hydrogen production. The asymmetric Ni–O–Ti sites prevent the formation of toxic byproducts such as cyanate and nitrite, ensuring the stability of the electrochemical system over extended periods. The study also demonstrates the effectiveness of these sites in converting urea to N₂ with high selectivity and efficiency, offering a sustainable solution for wastewater treatment and hydrogen production. The results highlight the potential of asymmetric Ni–O–Ti sites for practical applications in renewable energy and environmental remediation.This study presents a highly selective electrochemical urea oxidation reaction (UOR) with efficient hydrogen evolution, achieved through atomically isolated asymmetric Ni–O–Ti sites on a Ti foam anode. These sites exhibit a 99% nitrogen selectivity for urea oxidation, surpassing previously reported Ni-based electrocatalysts with selectivities below 55%. The asymmetric sites, featuring oxygenophilic Ti adjacent to Ni, favor interaction with the carbonyl group in urea, preventing premature C=N bond breakage and enabling selective intramolecular N–N coupling to N₂. The system also delivers a hydrogen evolution rate of 22.0 mL h⁻¹ when coupled to a Pt cathode under 213 mA cm⁻² at 1.40 V_RHE. A prototype device powered by a commercial Si photovoltaic cell is developed for solar-powered on-site urine processing and decentralized hydrogen production. The asymmetric Ni–O–Ti sites prevent the formation of toxic byproducts such as cyanate and nitrite, ensuring the stability of the electrochemical system over extended periods. The study also demonstrates the effectiveness of these sites in converting urea to N₂ with high selectivity and efficiency, offering a sustainable solution for wastewater treatment and hydrogen production. The results highlight the potential of asymmetric Ni–O–Ti sites for practical applications in renewable energy and environmental remediation.