Linear and nonlinear optical (NLO) polymeric materials with good processabilities are discussed. An azo-dye substituted copolymer (3RNO2, nitro-terminated diazo dye) are investigated. The polymer film was found to be transparent and attenuation loss was less than 2 dB/cm. The χ(3) of 3RNo2 reaches 5×10−11 esu in the near-resonant region. With polymers where the dye molecules are introduced into the polymer backbone (a main chain polymer), a χ(3) larger than 10−11 esu is obtained even in a monoazo dye introduced polymer. A new molecular crystal, symmetrically substituted benzylidene-aniline compound, SBAC for short, are also successfully polymerized (introduced into a polymer main chain) and their χ(3) values are revealed to be around 1010 esu in the near-resonant wavelength region. The optical transmission of these polymers is also investigated and revealed to be around 2 dB/cm. With poly(arylene vinylene), a certain population of χ-conjugation length will induce enhancement of the resonant χ(3) of the polymers. The polymer can be used to fabricate channel waveguides with the photo-bleaching technique.