The methacrylic monomers containing azobenzene moiety with flexible alkyl spacers of different lengths and groups of different nature are synthesized, and their physicochemical properties were determined by electronic absorption, (1)H spectroscopy, and element analysis. In the present work, the homopolymers built with the use of the free radical polymerization of methacrylic monomers incorporating an azobenzene side-group have been synthesized and structurally characterized. The results of photochemical and optical activities of the Corresponding polymers are presented. Third-order nonlinear optical (NLO) properties of the azopolymer solutions are studied by the degenerate four wave mixing (DFWM) method.