This study demonstrates the development of atomically isolated asymmetric Ni–O–Ti sites on a Ti foam anode, which achieve a nitrogen (N₂) selectivity of 99% for the electrochemical urea oxidation reaction (UOR). This surpasses the N₂ selectivity of connected symmetric Ni–O–Ni sites in previously reported Ni-based electrocatalysts, which are typically below 55%. The asymmetric Ni–O–Ti sites prevent the premature breakage of the C≡N bond in urea, favoring intramolecular N–N coupling to form N₂. This is achieved by strengthening the resonance between the NH₂ and C=O groups through electron donation from the oxygenophilic Ti adjacent to the Ni. The asymmetric sites also prevent the formation of cyanate (NCO⁻) and nitrite (NO₂⁻) species, ensuring the stability of the electrochemical system over extended periods. The prototype UOR–HER device, powered by a commercial Si photovoltaic cell, can efficiently process urine and produce hydrogen (H₂) and N₂, offering a sustainable solution for wastewater denitrification and decentralized H₂ production.This study demonstrates the development of atomically isolated asymmetric Ni–O–Ti sites on a Ti foam anode, which achieve a nitrogen (N₂) selectivity of 99% for the electrochemical urea oxidation reaction (UOR). This surpasses the N₂ selectivity of connected symmetric Ni–O–Ni sites in previously reported Ni-based electrocatalysts, which are typically below 55%. The asymmetric Ni–O–Ti sites prevent the premature breakage of the C≡N bond in urea, favoring intramolecular N–N coupling to form N₂. This is achieved by strengthening the resonance between the NH₂ and C=O groups through electron donation from the oxygenophilic Ti adjacent to the Ni. The asymmetric sites also prevent the formation of cyanate (NCO⁻) and nitrite (NO₂⁻) species, ensuring the stability of the electrochemical system over extended periods. The prototype UOR–HER device, powered by a commercial Si photovoltaic cell, can efficiently process urine and produce hydrogen (H₂) and N₂, offering a sustainable solution for wastewater denitrification and decentralized H₂ production.