Indolizidines are bioactive heterocyclic compounds of great potential normally prepared following multistep routes. However, to the best of our knowledge, the synthesis of 1-aminoindolizidines has never been reported. Herein, 1-(dialkylamino)-3-substituted indolizidines have been straightforwardly synthesized using an atom-economic protocol that involves a copper-catalyzed three-component synthesis of indolizines followed by heterogeneous catalytic hydrogenation. The latter was found to be chemoselective using platinum(IV) oxide as the catalyst at 3.7 atm, providing the aminoindolizidines in modest-to-high yields (35-95%) and high diastereoselectivity (92:8 to >99:1). It has been experimentally demonstrated that the hydrogenation occurs through the intermediate 5,6,7,8-tetrahydroindolizine, which contains a pyrrole moiety. Moreover, the diastereomerically pure 1-(dibenzylamino)-3-substituted indolizidines could be further transformed into the corresponding monobenzylated or fully debenzylated aminoindolizidines by selective hydrogenolysis catalyzed by Pt/C or Pd/C, respectively, under ambient conditions.