Transition metals have been recognized as excellent and efficient catalysts for the electrochemical nitric oxide reduction reaction (NORR) to value-added chemicals. In this work, a class of core-shell electrocatalysts that utilize nickel nanoparticles in the core and nitrogen-doped porous carbon architecture in the shell (Ni@NC) for the efficient electroreduction of NO to ammonia (NH3) is reported. In Ni@NC, the NC prevents the dissolution of Ni nanoparticles and ensures the long-term stability of the catalyst. The Ni nanoparticles involve in the catalytic reduction of NO to NH3 during electrolysis. As a result, the Ni@NC achieves a faradaic efficiency (FE) of 72.3% at 0.16 V-RHE. The full-cell electrolyzer is constructed by coupling Ni@NC as cathode for NORR and RuO2 as an anode for oxygen evolution reaction (OER), which delivers a stable performance over 20 cycles at 1.5 V. While integrating this setup with a PV-electrolyzer cell, and it demonstrates an appreciable FE of >50%. Thus, the results exemplify that the core-shell catalyst based electrolyzer is a promising approach for the stable NO to NH3 electroconversion.