We performed the synthesis, spectroscopic and electrical characterization of poly(2-bromo-5-hexyloxy-p-phenylenevinylene), BHPPV, and poly(5,5'-dibromo-2,2'-bis-hexyloxy-4,4'-biphenylenevinylene), BHBPV. We determined the positive charge carrier mobility, similar to 3.7 x 10(-7) cm(2) V-1 S-1 for BHPPV and 5.9 x 10(-7) cm(2) V-1 s(-1) for BHBPV and estimated the energy levels, energy gap and determined the photoluminescence spectrum for both polymers. The results are compared with similar results on poly(p-phenylenevinylene) and poly(biphenylenevinylene) derivatives, discussing trends in physical parameters. (c) 2005 Elsevier B.V. All rights reserved.