The fourth generation of a dendritic polyphenylazomethine (DPA 134) has 2, 4, 8, and 16 imine groups in the first, second, third, and fourth shells, respectively (total, 30 imine groups). DPA G4 can trap 30 equiv of SnCl2 molecules, because the imine group is complexed with SnCl2 at a ratio of 1:1. During addition of 30 equiv of SnCl2 to DPA G4, four shifts in the isosbestic point were observed in the UV-vis spectra, and the amount of SnCl2 added in each step is in agreement with the number of imine groups in each shell of DPA G4. This result shows that the complexation of the imine groups in DPA G4 with SnCl2 occurs stepwise in the order of the first, second, third, and fourth shells. The unique stepwise complexation was also observed in DPA G2 and G3 as two and three shifts of the isosbestic point, respectively. The stepwise complexation was supported by TEM, NMR, and a novel shell-selective reduction (SSR) method for imines. An expansion in the molecular size of DPA G4 by the complexation was revealed by molecular modeling and TEM measurements. The stepwise complexation is caused by the different basicity of the imine groups between the shells, which was supported by the chemical shifts of the peaks attributed to the imine carbons in the C-13 NMR spectra. The gradients in the basicity were controlled by the introduction of electron-withdrawing or -releasing groups to the core of the dendrimers; the core imines were complexed last in DPAs having a 2,3,5,6-tetrafluoro or 2,5-dichlorophenyl core due to the low basicity of the core imines. The different complexation pattern was also clearly confirmed by the SSR method.