<p>Cu-based materials show great potential in electrocatalytic CO₂ reduction due to their excellent ability to produce C₂₊ products. Among them, Cu-based metal-organic framework (MOF) materials have gained widespread attention because of their highly tunable structures. However, the poor conductivity and stability of MOF materials in electrocatalysis are significant barriers to large-scale CO₂ conversion. To overcome these challenges, this study used a simple and scalable one-pot method to incorporate the electron-rich ligand 1,1’-Ferrocenedicarboxylic acid (Fc) into Cu-BTC (1,3,5-Benzenetricarboxylic acid). This approach regulated the local electron density near the metal center and lowered the energy barrier for C-C coupling, which increased the selectivity for C₂₊ products. In the KHCO₃ buffer system, the Faradaic efficiency of C₂₊ products (FE_C2+) under Cu-BTC-Fc _(0.2) catalysis reached 55% at -1.05&#xa0;V (vs. RHE), significantly higher than unmodified Cu-BTC. Meanwhile, the KCl non-buffered system suppressed hydrogen evolution, thereby improving the selectivity for the single C₂₊ product ethylene. Additionally, comparing the catalyst’s properties before and after electrochemical polarization shows that the elemental composition and crystal structure of Cu-BTC-Fc_(x) remained relatively unchanged, and the valence state of copper ions kept stable during the reaction. This suggests that the material demonstrated high electrocatalytic activity and excellent electrochemical stability, which could support the advancement and application of electrocatalytic CO₂ reduction technology.</p>