A copper complex, [Cu-I(tmpa)(MeCN)](+), effectively reductively couples NO(g) at RT in methanol (MeOH), giving a structurally characterized hyponitritodicopper(II) adduct. Hydrogen-bonding from MeOH is critical for the hyponitrite complex formation and stabilization. This complex exhibits the reverse redox process in aprotic solvents, giving Cu-I + NO(g), leading to Cu-I-mediated NO(g)-disproportionation. The relationship of this chemistry to biological iron and/or copper mediated NO(g) reductive coupling to give N2O(g) is discussed.