A new series of aromatic azobenzol compounds containing vinyl have been designed as monomers. The azobenzene-containing side-chain polymers containing azo NLO chromophore in each side chain have been synthesized via free radical polymerization. FT-IR, elemental analysis and 1 H NMR were performed to characterize the azo monomers. The molecular weight of the polymers and their distribution were determined by gel permeation chromatography (GPC). The third-order NLO coefficient of azo monomers and their polymers were measured by degenerated four wave mixing (DFWM) technique. As a result, the enhancement of the molecular conjugation and the increase of the NLO chromophore concentration in the molecular chain contribute much to heightening the third-order NLO effect. The electronic effect of substituent on the azobenzol group and the push–pull electronic structure contributes much to enhancing the NLO property.