Abstract Electrochemical reduction of carbon dioxide is a clean and highly attractive strategy for the production of organic products. However, this is hindered severely by the high negative potential required to activate carbon dioxide. Here, we report the preparation of a copper-electrode onto which the porous metal–organic framework [Cu2(L)] [H4L = 4,4′,4″,4′′′-(1,4-phenylenebis(pyridine-4,2,6-triyl))tetrabenzoic acid] can be deposited by electro-synthesis templated by an ionic liquid. This decorated electrode shows a remarkable onset potential for reduction of carbon dioxide to formic acid at −1.45 V vs. Ag/Ag+, representing a low value for electro-reduction of carbon dioxide in an organic electrolyte. A current density of 65.8 mA·cm−2 at −1.8 V vs. Ag/Ag+ is observed with a Faradaic efficiency to formic acid of 90.5%. Electron paramagnetic resonance spectroscopy confirms that the templated electro-synthesis affords structural defects in the metal–organic framework film comprising uncoupled Cu(II) centres homogenously distributed throughout. These active sites promote catalytic performance as confirmed by computational modelling.