The activation and functionalization of dinitrogen with carbon dioxide into useful chemicals containing C-N bonds are significant research projects but highly challenging. Herein, we report that N 2 molecules are dissociated by heterobimetallic CuNb − anions assisted by surface plasma radiation, leading to the formation of CuNbN 2 − anions; the CuNbN 2 − anions can further react with CO 2 to generate products NCO − with one C-N bond and NbO 2 NCN − with two C-N bonds under thermal collision conditions. For the activation of dinitrogen, the plasma atmosphere is conducive to the dissociation of the N&z.tbd;N bond, which renders the coupling reactions of N 2 and CO 2 molecules easier to proceed. This is the first report of coupling of N 2 and CO 2 to generate C-N bonds by making good use of the plasma effect to assist in the activation of N 2 molecules. This new strategy with the assistance of plasma provides a practicable route to construct C-N bonds by directly using N 2 and CO 2 at room temperature. Plasma effect promotes the dissociation of N&z.tbd;N bonds on the heterobimetallic anion CuNb − , leading to the formation of CuNbN 2 − . CuNbN 2 − further reacts with CO 2 to obtain NCO − , therefore N 2 and CO 2 coupling reaction is realized at room temperature.