Asymmetric and color tunable poly(p-phenylene vinylene) (PPV) derivatives with a dimethyldodecylsilylphenyl pendant group, poly[2-(3‘-dimethyldodecylsilylphenyl)-1,4-phenylene vinylene] (m-SiPhPPV) and poly[2-(3‘-dimethyldodecylsilylphenyl)-1,4-phenylene vinylene-co-2-methoxy-5-(2‘-ethylhexyl oxy)-1,4-phenylene vinylene] (m-SiPhPPV-co-MEH−PPV), have been synthesized by a dehydrohalogenation method. Newly synthesized, these homo- and copolymers are highly soluble in common organic solvents. The defect-free uniformly thin films easily formed onto the indium tin oxide (ITO) coated glass substrate. The resulting polymers had high molecular weights with narrow polydispersities and high thermal stability up to 400 °C. The copolymers showed better optical and electroluminescent (EL) properties than those of the homopolymer. Single-layer light-emitting devices with an ITO/polymer/Al:Li alloy configuration were fabricated by using the resulting polymers. The maximum EL emissions of m-SiPhPPV and m-SiPhPPV-co-MEHPP...