Upgrading nitrogen to ammonium fertilizer under environmental conditions presents a promising prospect for the application of distributed renewable energy. Herein, a hybrid plasma-electro-membrane triple intensified system is developed to achieve ammonium fertilizer synthesis. Initially, the air undergoes a transformation into NO2− by plasma. Then, the PdNPs/Fe-N-C, which is composed of palladium nanoparticles (PdNPs) and iron single atoms (Fe-N-C), was employed as the catalyst for the NO2− electroreduction reaction (NO2−RR), exhibiting a remarkable NH3 yield rate of 92.7 mg h−1 mgcat−1, corresponding to a Faradaic efficiency (FE) of nearly 100%. Experimental and theoretical analysis showed that Fe-N-C is the active site of NO2− reduction, and the PdNPs can dissociate water to produce adsorbed hydrogen for nitrogen intermediate reduction. The electron transfer between PdNPs and the Fe-N-C makes the spin configuration of Fe change from low to medium spin state, therefore decreasing the energy barrier of the *NO hydrogenation process during NO2−RR. Finally, the NH3-containing electrolyte is passed through a membrane separation reactor optimized for mass transfer to achieve NH3 recovery and ammonium fertilizer synthesis. The PdNPs/Fe-N-C driven hybrid system achieves a high (NH4)2SO4 yield of 685.8 mg h−1, which can also be applied to the synthesis of other ammonium fertilizers.