Phenylazomethine dendrimer (DPA) is a dendritic ligand that coordinates to various Lewis acids in a stepwise radial fashion. Second generation para-substituted and meta-substituted phenylazomethine dendrimers with p-phenylenediamine and m-phenylenediamine core were synthesized and the coordination sequence was investigated by UV–vis titration. Stepwise radial complexation from the outer layer was observed for the m-phenylenediamine core meta-substituted phenylazomethine dendrimer (m-mG2). Other three dendrimers showed stepwise radial complexation from the inner layer. The reason could be explained with the binding constant of the 1st generation dendrimer (model of the 1st layer). This is suggesting that for controlling the coordination sequence of DPA, not only the dendron structure is important, but also the structure of the core is an important factor.