A series of dendritic phenylazomethines (DPA), which have a meso-substituted zinc porphyrin core (DPAGX-ZnP, X = 1-4), were synthesized. Structural studies of these dendrimers were carried out using Tri-SEC (triple detection after size exclusion chromatography), intrinsic viscosity analysis, TEM (tunneling electron microscopy), and molecular modeling calculations by AM1. As a result, a sphere-like structure within a single-nanometer scale (R(h) = 22 A for DPAG4-ZnP) was observed. In addition, encapsulating effects by the DPA shell in the larger dendrimers were confirmed as fundamental properties, based on the UV-vis abosorption spectra, cyclic voltammograms, and 1H NMR spin-lattice relaxation times (T1). The DPAGX-ZnP acts as a multi-metal ion reservoir for SnCl2 and FeCl3. The generation-4 dendrimer (DPAG4-ZnP) can take up to 60 molar amounts of metal complexes around the porphyrin core. A quantitative study of the metal assembling reaction by UV-vis titration revealed stepwise layer-by-layer complexations from the inner imines nearest to the core to the surface. The redox behavior and fluorescence of the zinc porphyrin in these metal-assembled dendrimers also support the stepwise complexation of the metal ion. These analyses suggest that the finely assembled metal complexes in a dendrimer architecture strongly affect the electronic status of the porphyrin core. Results from transient absorption measurements strongly indicate a very fast electron transfer on a subpicosecond time scale between the core and assembled metal complexes.