The eight-electron transfer pathway required for CH₄ formation in eCO₂RR is kinetically slow, which leads to poor reaction selectivity. In this work, a CuZn-BDC-NH₂ precursor was synthesized via a facile solvothermal method, and a series of CuZn@C materials were prepared by calcination under varying temperature conditions (700°C, 800°C, 900°C) utilizing the high-temperature volatility of Zn. Among them, the CuZn800@C sample demonstrates the best CH₄ electro-reduction performance, achieving a methane Faradaic efficiency (FE) of 64.5% and a partial current density of -429.1 mA/cm² at a potential of -1.7 V vs. RHE, along with excellent stability, showing only a slight performance decline after a 24-hour test. Through in situ infrared spectroscopy and DFT calculations, electrocatalytic mechanism investigations reveal that Zn and Cu form a tandem reaction system. Zn sites promote water splitting to provide protons, while Cu sites reduce the energy barrier for *CO hydrogenation. Moreover, Zn and Cu can constitute dual active sites that enhance CO₂ adsorption, thereby boosting subsequent reactions. This work develops a new strategy for designing high performance Cu-based methanation catalysts.