A triply fused tetracyclic macromolecular K-3,K-3 graph has been constructed through electrostatic self-assembly of a uniformly sized dendritic polymer precursor having six cylic ammonium salt end groups carrying two units of a trifunctional carboxylate counteranions, and subsequent covalent conversion by the ring-opening reaction of cyclic ammonium salt groups at an elevated temperature under dilution. The K-3,K-3 graph product was isolated from the two constitutional isomers by means of a recycling SEC technique, as the hydrodynamic volume of the triply fused tetracyclic K-3,K-3 product is remarkably contracted in comparison with another isomer having a ladder form in solution.