Herein we report the solventless synthesis and doping of the benchmark HKUST-1(Cu) as a facile route to afford heterometallic metal–organic frameworks (MOFs) having proficient behavior as electrocatalytic materials in the reduction of carbon dioxide. Zn(II), Ru(III) and Pd(II) were selected as doping metals (MD) with the aim of partially replacing the Cu(II) atoms of the pristine structure to afford HKUST-1(Cu,MD) type materials. Apart from the high yield and good crystallinity of the obtained materials, the extremely high reagent concentration that the reaction conditions imply makes it feasible to control dopant loading in all cases. Prepared samples were processed as electrodes and assembled in a continuous flow filter-press electrochemical cell. Faraday efficiency to methanol and ethanol at Ru(III)-based electrodes resulted in activity as high as 47.2%, although the activity of the material decayed with time. The interplay of the dopant metal and copper(II), and the long-term performance are also discussed.