The mechanism of CO2 capture on the nitrate and nitrite anion species synergistic promoted MgO has been rarely studied and still not fully understood. Herein we report a systematic investigation on the CO2 adsorption performance of molten salts-promoted MgO adsorbent to deeply reveal the synergistic promoted mechanism of nitrate and nitrite. A series of MgO-based solid adsorbents were synthesized and applied for CO2 capture using NaNO2/KNO3 as promoters. The addition of mixed nitrate and nitrite promoters greatly enhances the adsorption capacity of MgO, exhibiting CO2 capture up to 10.25 mmol·g−1 under optimal conditions. The MgO-based adsorbent in the form of nanosheets has faster adsorption kinetics and better stability, and the possible reaction mechanism of MgO modified by nitrate and nitrite was proposed. Firstly, NO3– interacts with the lattice oxygen (O12-) of MgO to form NO2– and O22–. Secondly, Mg2+ interacts with the free NO2– to form [Mg···NO2]+ and further overcomes the energy barrier to generate [Mg2+···O2–] ion pairs. O22– is not stable and prone to side reaction. However, NO2– can be converted into O2–, and O2– is further generated to O22–, facilitating regeneration of NO3–. The introduction of molten salt can significantly reduce the reaction energy barrier, and the energy barrier required to generate [Mg2+···O2–] ion pairs is reduced from 6.86 eV to 3.50 eV. Adsorption kinetics studies reveal that the nano-flake MgO facilitates the full contact with the promoter and has faster reaction kinetics in the surface reaction control stage. These insights into the synergistic promoted mechanism of nitrate and nitrite anion species is expected to provide guidance for the further design of the high performance MgO-based CO2 adsorbent.