Abstract: A novel electroluminescent polymer, Poly (2-Pentyloxy-3,5-Dibromine-1,4-Phenylenevinylene) (PPDBPV) was prepared by the Gilch route. It is so hard to get new precursor by the traditional route because of the inactivation on benzene ring causing by electron withdrawing effect. To resolve the problem, a modified route has been prepared. The polymer and monomers were characterized by 1H-NMR and FT-IR. The synthesis craft had been studied. The maximum Photoluminescence (PL) wavelength of PPDBPV appeared at 650 nm and gave 20 nm red shift comparing with Poly (2-Methoxy-5-Pentyloxy-1,4-Phenylenevinylene) (PMPPV).