We synthesized a branched poly(phenylene ethylene) (BPPE) with bromomethyl groups from 1,3,5-tris(bromomethyl)benzene derivatives via the Wurtz coupling reaction. In the case of 1,3,5-tris(bromomethyl)-2,4,6-trimethoxybenzene as a monomer, the obtained polymer (Mn = 6100, Mw/Mn = 1.9) had bromomethyl groups. The 1HNMR analysis showed that a very large number of unreacted bromomethyl groups (Ph-CH2Br) remained in the BPPE; the reaction of this polymer with phenolic hydroxyl groups proceeded quantitatively. This suggested that BPPEs can be functionalized using unreacted bromomethyl groups, making them a very attractive starting point for the creation of functionalized BPPEs with further enhanced processability. (c) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012