We utilized the first metathesis reaction to synthesize a new type of photorefractive polymers that contain both a carbazole moiety as a hole transporter and NLO chromophores, attached to π-conjugated backbones. These polymers show two maximum values of photocurrent around 350 and 700nm.The electro-optic coefficient (r33) of the poled polymer films measured at the wavelength of 1.3 μmwas in the value of 10.1pm/V. The nonresonat values of the third-order NLO coefficient, χ(3), of the resulting polymers were found to be 2.9 × 10−32esu.at the incident wavelength of 1.907 μm.