Substituted epoxy alcohols and amines allow for substrate- controlled conversion of CO2 into a wide range of heterocyclic structures through different mechanistic manifolds. This new approach allows for an unusual scope of CO2 derived products by initial activation of CO2 through the amine or alcohol unit, providing nucleophiles for intramolecular epoxy ring-opening under mild reaction conditions. Control experiments support the crucial role of the amine/alcohol fragment in this process with the nucleophile assisted ring-opening step following an SNi pathway and a 5-exo-tet cyclization leading towards heterocyclic scaffolds.