The present work aims to investigate the effect adding Ag, Co, Ni, Cd and Pt to copper on ethanol dehydrogenation. The catalysts synthesized by deposition–precipitation method were characterized using various physicochemical methods such as N2 adsorption–desorption, TPR, SEM–EDX, XRD, XPS and TGA–DSC-MS. Catalytic evaluation results revealed that the predominant product of the reaction was acetaldehyde. Monometallic copper or mixed with Cd, Ag or Co show good catalytic performances. Adding nickel to copper improves the process conversion but reduces acetaldehyde selectivity, giving rise to methane in produced hydrogen. Pt-Cu/SiO2 catalyst guides the reaction towards diethyl ether. Time on stream tests performed during 12 h at 260 °C, showed that adding Cd to Cu enhances its stability by over 30% of conversion, this is explained by the reduction of copper crystallites sintering, which makes Cd-Cu/SiO2 a promising catalyst for the production of acetaldehyde by ethanol dehydrogenation.