A supramolecular method to control the branched topology of polymerized product from the A
2+ B
4 reaction system has been developed. Depending on the feed ratio, the polycondensation-addition ofdivinylsulfone (DV, an A
2 monomer) and hexamethylenediamine (HDA, a B
4 monomer) gives a highly branchedpolymer (DV/HDA = 1:1) or chemical cross-linking gel (DV/HDA = 2:1). By introduction of
-cyclodextrin(
-CD) into this reaction system, the HDA molecule is selectively encapsulated into the cavity of
-CD.Interestingly, one hydrogen atom of each primary amino group in HDA molecule is physically protected by theCD cavity, so the dendritic unit (HDA molecule) is transformed into a linear unit through the inclusioncomplexation. Therefore, by merely adjusting the amount of
-CD, a cross-linking gel, hyperbranched polymer,highly branched polymer, slightly branched polymer, or linear polymer can be obtained, respectively. In short,the branched topology of the polymerized product from the A
2 + B
4 reaction system can be easily controlled byusing this supramolecular approach.