As the main nitrogen-containing pollutant of industrial and agricultural wastewater, ammonium (NH4+) is obtainable from the natural nitrogen cycle and industrial emission. Electrochemical recovering nitrogen (N) from nitrate-polluted wastewater to produce ammonia (NH3) is a promising route to mitigate pollution risks and create economic values. Since side reactions at the electrodes are inevitable, and the competition mechanism between electric double layer capacitance (EDLC) behavior and side reactions is still unclear. Herein, electrochemical selective NH4+ recovery from wastewater was achieved by coupling NH4+ adsorption and side oxygen reduction reaction (ORR) in a novel electrochemical membrane extraction system using Ti3C2TX-based gas-diffusion cathodes. Batch experiments showcase simultaneous NH4+ removal and recovery, with TiOX/TiC-C exhibiting the highest removal capability of 408 mgN g−1. In situ Raman spectroscopy revealed the critical role of the four-electron transfer ORR reaction in the conversion of NH4+ to NH3. Density functional theory (DFT) showed that excellent electron-donating ability for NH4+ of TiOX/TiC-C electrode (1.97 eV) facilitated NH4+ diffusion onto electrode interface. The study sheds light on the intricate interplay between NH4+ adsorption and ORR, highlighting the significance of tailored support and vacancy engineering in advancing wastewater treatment and resource recovery.