In the past, dendritic polyphenylazomethines (DPA) have been synthesized via the convergent method. However, the convergent method has problems such as difficult terminal-group modifications and an increased number of steps. Therefore, we synthesized the terminal-protected DPA to construct the dendritic structure via the divergent method. The combination of the convergent method and the divergent method easily achieved the rapid synthesis of a higher generation dendrimer. Furthermore, we succeeded in the synthesis of the water-soluble PEG-DPA via the divergent method using the ester-DPA.