Polymers based on N-phenyl maleimide, N-4-propargyl methoxy phenyl maleimide and methyl methacrylate was synthesized. High glass temperatures 183, 179, 159°C respectively for P1, P2 and P3 were achieved. EO polymer P3–C1, P3–C2 and P3–C3 with about 30wt% chromophore loading density were prepared by attaching Chromophore C1, C2 and C3 to polymer P3 using copper-catalyzed Huisgen cycloaddition reactions in mild reaction conditions and high yield. Among the EO polymers, P3–C3 showed us the best solubility in normal solvents and suitable glass temperature. EO films based on EO polymer P3–C3 showed us large EO coefficient of 50pm/V @1310nm and good long-term stability, 85% EO activity was kept after annealing at 85°C for 200h.