We synthesized poly(9,10-anthryleneethynylene)s bearing benzyl ether dendrimers with alkoxy peripheral groups at the 2- and 6-positions of anthracene by polymerization of the corresponding dibromoanthracenes and bis(3-hydroxy-3-methylbutynyl)anthracenes in the presence of a Pd(PPh3)4 catalyst and an appropriate base. The average degree of polymerization reached DPn = 50 by improving the solubility of poly(anthryleneethynylene)s. The UV–vis and CD spectra of poly(9,10-anthryleneethynylene)s bearing chiral menthoxy groups in addition to the dendritic side groups proved their ordered aggregation state in solution.