The　electrochemical　reduction　of　CO2　has　been　recognized　as　one　of　the　best　strategies　to　reduce　atmospheric　CO2　levels　and　achieve　a　carbon-neutral　economy.　We　report　here　a　copper　complex,　Cu(salan)2,　as　an　efficient　CO2　reduction　catalyst　in　basic　aqueous　media.　Cu(salan)2　exhibited　different　catalytic　behaviors　in　nanocrystalline　and　graphene-supported　forms.　As　nanocrystals,　the　complex　did　not　show　high　catalytic　activity　and　gradually　decomposed　into　Cu2O　upon　electrolysis.　However,　when　dispersed　on　a　graphene　matrix,　Cu(salan)2　exhibited　a　moderate-to-high　CO　selectivity　and　remained　stable　in　long-term　electrolysis.　This　work　shows　that　site-isolation　by　dispersion　of　a　molecular　catalyst　is　an　effective　way　to　increase　the　catalyst　stability　and　tune　the　product　selectivity　for　CO2RR　electrocatalysis.　©　2022　Wiley-VCH　GmbH.