Substituted epoxy alcohols and amines allow substrate-controlled conversion of CO₂ into a wide range of heterocyclic structures through different mechanistic manifolds. This new approach results in an unusual scope of CO₂-derived products by initial activation of CO₂ through either the amine or alcohol unit, thus 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 S_Ni pathway, and a 5-exo-tet cyclization, thus leading to heterocyclic scaffolds.