A heterotritopic copillar5]arene monomer by introducing effective neutral guest moieties (methylene chains end‐capped with cyano and triazole groups) to a pillar5]arene macrocycle is prepared. This well‐designed AB2‐type copillar5]arene contains strong host–guest recognition motifs that are connected with relatively flexible and long linkers, thus efficiently assembles to form supramolecular hyperbranched polymer (SHP) in chloroform solution, which is characterized by various techniques including 1H NMR, DOSY, viscosity, DLS, and TEM. Particularly, this supramolecular polymer can be effectively depolymerized by adding a competitive butanedinitrile guest.
