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 of divinylsulfone (DV, an A(2) monomer) and hexamethylenediamine (HDA, a B-4 monomer) gives a highly branched polymer (DV/HDA = 1:1) or chemical cross-linking gel (DV/HDA = 2:1). By introduction of beta-cyclodextrin (beta-CD) into this reaction system, the HDA molecule is selectively encapsulated into the cavity of beta-CD. Interestingly, one hydrogen atom of each primary amino group in HDA molecule is physically protected by the CD cavity, so the dendritic unit (HDA molecule) is transformed into a linear unit through the inclusion complexation. Therefore, by merely adjusting the amount of beta-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 by using this supramolecular approach.