In　this　study,　an　organocatalytic　ring-opening　polymerization　(ROP)　of　ϵ-caprolactone　(ϵ-CL)　has　been　developed　by　employing　PADIs　as　a　novel　and　efficient　acid/base　bifunctional　organocatalyst,　which　could　afford　metal-free　poly(ϵ-caprolactone)　with　predictable　molecular　weight　and　narrow　dispersity　at　a　low　catalyst　loading　under　mild　conditions.　NMR　and　kinetic　studies　indicate　that　the　ring-opening　polymerizations　of　lactones　catalyzed　by　PADIs　proceed　in　a　living　and　well　controlled　manner.　Moreover,　this　organic　Brønsted　acid　catalytic　system　could　allow　the　synthesis　of　PCL　with　molecular　weight　above　60　kg/mol,　as　well　as　well-defined　star　polymers.　©　2022　Wiley-VCH　GmbH.