1,4-Di-alpha -bromomethyl-2,3,5,6-tetrafluorobenzene (1) was prepared from the bromination of 2,3,5,6-tetrafluoro-p-xylene. The product was carefully purified and analyzed by GC/MS, HPLC, FTIR, and H-1 NMR. The structure of I was unequivocally confirmed by the X-ray diffraction method. The melting point of 126 degreesC for I was vastly different from the previously reported value of 68-70 degreesC. Poly(2,3,5,6-tetrafluorophenylenevinylene) (PTFPV) homopolymer was successfully prepared via the bromine precursor route (BPR). The polymer showed excellent photoluminescence with emission maxima at shorter wavelengths of 485 and 515 nm. The single-layer device of ITO/PTFPV/Al configuration emitted green light at low turn-on voltage of about 4.2 V. The results demonstrated that PTFPV prepared via BPR was a good emitting material for the LEDs in the green-blue region.