Dendritic polyphenylazomethine (DPA) stepwisely complexes with metal ions based on the interaction between a Lewis acid and base. DPA has pi-conjugated rigid backbones, which are suitable for delocalization of cation charges. In this study, triphenylmethylium (TPM) could coordinate to the imine group of the fourth generation of DPA (DPAG4, DPAGX, designated GX, where Xis the generation number) in a stepwise radial fashion, which allows control of the number and position of TPM on a dendrimer as metal ions do. For the detailed investigation of TPM precise assembly, this paper have shown that DPAG4-ZnP, a porphyrin core phenylazomethine dendrimer having 60 imine sites, could complex with TPMs in a stepwise fashion similar to that of p-phenylene core DPAG4 having 30 imine sites. In addition, the investigation of the hybrid assembly using TPM and metal ions on DPAG4 was performed. We confirmed that the inner layer of DPAG4 was complexed with TPM, followed by the outer layer with SnCl2. This study developed the range of controlling precise assembly on a DPA mold. The process of TPM assembly was analyzed using UV-vis spectroscopy, NMR, free volume, and cyclic voltammetry.