Weakly electron withdrawing bromine substituted poly(2-bromo-1,4-phenylenevinylene) (PBrPV) was synthesized th-rough water-soluble precursor method. The linear and nonlinear optical properties of PBrPV were compared with those of poly(1,4-phenylenevinylene) (PPV). The third-order nonlinear optical susceptibility, X^{(3)}$, was measured by using third-harmonic generation (THG) technique at 1907 nm, fundamental wavelength. The calculated $X^{(3)}$ values of PPV and PBrPV were 3${ imes}$ 10$^{-12}$ esu and 2${ imes}$10$^{-12}$ esu, respectively.