New random copolymers of phenylsilyl- and alkoxy-substituted phenylenevinylene, DMPS(9)-MEH(1)-PPV, DMPS(5)- MEH(5)-PPV and DMPS(1)-MEH(9)-PPV, have been synthesized by the Gilch dehydrohalogenation route, and the light-emitting properties of these polymers have been studied. The synthesized polymers were completely soluble in common organic solvents, and exhibited good thermal stability, almost up to $380^{circ}C$. They showed UV-visible absorbance and photoluminescence (PL) in the ranges of 422-510 and 513-590 nm, respectively, according to their feed ratios. Electroluminescent devices were fabricated with these polymers as emitting layers, and ITO and Al as anode and cathode, respectively. DMPS(1)-MEH(9)-PPV, DMPS(5)-MEH(5)-PPV and DMPS(9)-MEH(1)-PPV exhibited EL emission maxima at 575 nm, 565 nm, and 541 nm, respectively.