This work theoretically demonstrates a catalyst of copper monatomic wire supported on graphene nanoribbons (Cu-GNR) with a high efficiency for nitric oxide electroreduction reaction (NORR). This not only decreases the usage rate of noble metals but also possesses superior limiting potential comparable to pure Cu (- 0.69 and - 0.61V, vs. reversible hydrogen electrode (RHE)). The key is that Cu-GNR will have more efficient catalytic activity for NORR when fully covered by NO, since these weaken the adsorption ability of the reduction steps at the beginning. In sum, our findings may offer a platform for clarifying the effects of the concentration of reactants on catalytic process. Spin-polarized DFT with ultrasoft pseudopotentials as implemented in the CASTEP code was used in this work. The exchange correlation effects were described by generalized gradient approximation (GGA) with Perdew-Burke-Ernzerhof (PBE) functional. The dispersion correction within Grimme scheme (DFT-D2) was employed to accurately describe the van der Waals (vdW) interactions. The Hirshfeld population analysis was adopted to evaluate the charge transfer.