<p>This research focuses on utilizing and evaluating copper(II) salen as an electrocatalyst for carbon dioxide (CO₂) electro-reduction, compared to other metal salen complexes, including cobalt(II) salen and nickel(II) salen. Copper(II) salen was successfully synthesized, characterized, and applied as a homogeneous electrocatalyst for the electro-reduction of CO₂ in non-aqueous solution. The efficiency of metal salen electrocatalysts and the effect of central metal ions were discussed. Among the salen complexes, copper(II) salen showed the best electrocatalytic activity for CO₂ electro-reduction by giving the highest current enhancement in cyclic voltammetric studies. Under the optimized applied potential and the presence of HFIP as a proton donor, controlled-potential electrolysis of CO₂ by electrogenerated copper(I) species yielded carbon monoxide and methane in the gas phase as well as formate ion and oxalate ion in the liquid phase. Furthermore, X-ray diffraction (XRD) analysis, scanning electron microscopy-energy dispersive X-ray (SEM-EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS) were employed to reveal the morphological and structural information of the electrocatalyst.</p> Graphical Abstract <p></p>