AbstractMulti‐walled carbon nanotubes (MWCNTs) were grown on a stainless steel mesh and decorated with nickel nanoparticles (Ni NPs). The developed Ni NP‐MWCNT material was then used as a cathode in an electrochemical batch reactor to electrocatalytically convert NAD+ to enzymatically‐active 1,4‐NADH. The regeneration of 1,4‐NADH was studied at various electrode potentials. At electrode potential of −1.6 V, a very high recovery (relative amount of 1,4‐NADH in the product mixture) was obtained, 98 ± 1 %. In comparison, to achieve the same recovery on a non‐decorated MWCNT cathode, a much higher cathodic potential was needed (−2.3 V), establishing the importance of Ni NPs on the electrocatalytic activity in reducing NAD+ to 1,4‐NADH. It was postulated that hydrogen adsorbs on Ni NPs immobilized on MWCNTs to form Ni‐Hads, and this activated hydrogen rapidly reacts with neighbouring NAD‐radicals, preventing the dimerization of the latter species, ultimately yielding 1,4‐NADH.