A new series of electro-optical dendrimers with asymmetric configurations was synthesized through a Cu(I) catalyzed Huisgen reaction. The asymmetric dendrimers exhibited weaker chromophore dipole-dipole aggregations along with an improved response to the applied poling field than traditional dendrimers with the same type of chromophores. In order to systematically investigate the influence of the asymmetric structure on the physical properties, UV-vis spectroscopy and DFT calculations were carried out. Due to the asymmetric configurations, the obtained dendrimers exhibited weak dipole-dipole interactions compared with dendrimers with a flexible linker, furthermore they obtained a better alignment in the poling process. The asymmetric dendrimer AD-2 exhibited a 36 pm V-1 EO coefficient measurement, which was higher than the other two dendrimers and guest-host polymeric materials using the same chromophores.