Two series of amphiphiles composed of hydrophilic poly(amidoamine) dendrons (from the first to the third generation) as the shell and hydrophobic aromatic chromophores (3,6-di(maleimidyl)-9-phenyl carbazole and 9-(4'-maleimidyl phenyl)-3-maleimidyl carbazole) as the central scaffold were synthesized. The effect of dendritic architecture on the photophysical properties and the self-assembly behavior of these amphiphiles were studied by UV-vis absorption spectroscopy, fluorescence spectroscopy, and transmission electron microscopy (TEM) measurements. Both the generation of dendritic shell and the location of dendrons at the chromophoric scaffold had great effect on the photophysical properties of these amphiphiles. In addition, different spherical aggregates were formed from these amphiphiles in the aqueous solution at different concentrations. Because of the combined effects of steric hindrance and architecture of dendritic shells, the amphiphiles from G2 dendron with central chromophore self-organized into ordered aggregates more readily than that from G1 and G3. (C) 2008 Wiley Periodicals, Inc.