The synthesis and characterization of four methacrylate copolymers obtained by radical addition polymerization of methyl methacrylate as well as a new methacrylate azophenylbenzoxazole chromophore in percentages of 10, 30, 50, and 70% were explored. The copolymers were amorphous and showed glass-transition temperatures ranging from132 to 146 °C. High-quality polymer films were easily obtained by spin coating from N-methylpyrrolidone solutions. Polymer films spun cast on iridium tin oxide (ITO) substrates were used in the electro-optic (EO) experiments to evaluate the EO coefficients r33 using the reflection technique. The measured values fell in the range of 1.7–3.7 pm/V (laser incident wavelength of 1.552 mm) depending on the percentage of chromophore in the polymer.