This communication describes the synthesis of a triple acid-functionalized RAFT agent and its use to prepare well-defined 3-arm star polymers of N,N-dimethylacrylamide (DMAc). A simple esterification reaction allowed the convenient integration of three electron-rich naphthalene recognition units on the RAFT agent platform and subsequently the elaboration of a naphthalene end-decorated telechelic 3-arm star PDMAc. This functionalized star polymer was further exploited to build a hydrogel with a complementary homoditopic host unit featuring tetracationic macrocycle cyclobis(paraquat-p-phenylene) units.