Heterocyclic monomers based on 2,1,3-benzooxadiazole and 2,1,3-benzothiadiazole bearing solubilizing side chains have been synthesized in high yields over three steps from readily available starting materials. The monomers are efficiently cross-coupled with diynes and bis(boronates) to afford high molecular weight luminescent poly(arylene ethynylene)s and polyfluorenes that exhibit red-shifted absorption and emission maxima, greater solubility, and reduced aggregation.