A new class of poly(p-phenyleneethynylene) (PPE) polymers, COU-OPPE and ANT-OPPE, have been prepared, in which coumarin- and anthracene-based sensitizer molecules are covalently linked to the conjugated polymer backbone via a flexible spacer. In dilute solutions of these polymers, efficient resonance energy transfer is observed from the sensitizer moieties to the PPE backbone, resulting in enhanced luminescence of the PPE macromolecules. Also, when incorporated as guests in oriented polyethylene films, the novel polymers, COU-OPPE and ANT-OPPE, show efficient energy transfer from the pendent sensitizer to the PPE backbone. Especially in the case of ANT-OPPE; we found that the PPE backbone is efficiently oriented while the anthracene moiety remains essentially isotropic, which results in a high degree of polarizing energy transfer for this system.