This work reports the selective electrochemical conversion of CO2 to methane, the reverse reaction of fossil fuel combustion. This reaction is facilitated by preactivation of the CO2 molecule with an N-heterocyclic carbene (NHC) to form a zwitterionic species in the first step. In the presence of Ni(cyclam)(2+) and CF3CH2OH, this species is shown to undergo further electrochemical reduction of the bound-CO2 fragment at glassy carbon cathodes in dichloromethane electrolyte solution. Labeling studies confirm the origin of the carbon and protons in the methane product are the preactivated CO2 and trifluoroethanol respectively. (C) The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. All rights reserved.