The first optically active polydendrimers have been synthesized by polymerization of binaphthyl-based dendrimers. Study of the chiral optical properties of the polydendrimers and their model compounds has revealed that the interaction of the dendritic side chains along the polybinaphyhyl backbone cannot induce a secondary helical conformation. Energy migration from the dendritic side chains to the more conjugated bolybinaphthyl main chain is observed through absorption and fluorescence spectroscopic studies. As the dendritic generation increases, the glass transition temperature of the polydendrimers decreases significantly, The dendritic substituents have made considerable influence on the thermal transition of the polybinaphthyls.