Brominated poly(bis(4-methylphenoxyphosphazene) was allowed to react with 1,4-bischloromethylbenzene or 1,4-bischloromethyl-2,5-dimethoxybenzene in solution using phase transfer catalyst or potassium t-butoxide. Poly(p-phenylene vinylene) or poly(2,5-methoxy-1,4-phenylene vinylene) grafted organophosphazene copolymers were obtained. The UV-Vis absorption, photoluminescent, and thermal properties of the copolymers were measured. The copolymers are complete soluble in common organic solvents and fluoresce in the blue color range. The copolymers were used to build a series of organic light emitting diode (OLED). Only weak to nominated intensities with emission color from blue to red were obtained. The photoluminescent and electroluminescent (EL) spectra indicated there is a distribution in the PPV conjugated length. The compositions of the copolymers before and after the graft reaction were analyzed using NMR.