Conjugated three- and four-arm star polymers were successfully prepared by palladium catalyzed one-pot Suzuki polycondensation of the multifunctional cores and an AB-type monomer. The molecular weight of the star polymers could be controlled by the feed ratios of the monomers. The bromo end groups could be completely modified by fluorene mono boronic acid or triphenylamine mono boronic ester. The investigation of the optical, electrochemical, and thermal properties of the star polymers was also reported. All polymers exhibited good thermal stabilities and all the TPA-capped polymers showed good hole-transport abilities.