Electrocatalysts for CO(2)electroreduction require not only high-performance active materials to control the series reaction but also conductive and durable supports to ensure long-term stability under harsh operating conditions. Instead of conventional heterogeneous catalysts made by attaching metal on supports, we manufactured a self-formed tandem catalyst designed for a cascade electroreduction of CO(2)to C2H4. Using oxygen partial pressure-controlled calcination, electrospun copper acetate/polyacrylonitrile nanofibers were successfully transformed into porous carbon nanofibers consisting of doped N and metallic Cu particles. Doped nitrogen atoms adjacent to Cu atoms trigger the reaction by increasing the amount of CO* on the Cu surfaces, which lowers the energy required for CO dimerization that is used for C(2)H(4)production. The Cu-embedded N-doped carbon nanofibers exhibit a C(2)H(4)faradaic efficiency of 62% at a potential of -0.57 Vvs.RHE with high current density of 600 mA cm(-2)and excellent long-term stability. DFT calculations suggest that the lowered overpotential originates from the decreased CO dimerization energy barrier due to the doped N triggering CO production around the Cu particles.