Two novel luminescent block copolymers (CE-PPV and CE-DMPPV), containing alternating distyrylbenzene [poly(phenylene vinylene) model oligomer] as light-emitting units and crown-ether segments as ionic conductive and spacer units were synthesized by use of a Wittig reaction between the dialdehyde monomer and 1,4-xylylene-bis(triphenylphosphonium bromide) or 1,4-bis(triphenylphosphoniomethyl)-2,5-dimethoxybenzene dichloride. The synthesized polymers were characterized with FTIR, H-1-NMR, UV-Vis, differential scanning calorimetry, and gel permeation chromatography. The number-average molecular weights were 6896 with a polydispersity index of 1.75 for CE-PPV, and 9301 with a polydispersity index of 2.474 for CE-DMPPV, respectively. The decomposition temperatures and the glass-transition temperatures were in the range of 395-411degreesC and 75-77degreesC, respectively. The electrochemical properties of the copolymers were evaluated and the highest occupied molecular orbital and the lowest unoccupied molecular orbit energy levels of the copolymers were estimated by cyclic voltammetry. Efficient light-emitting diodes were successfully fabricated. The synthesis, characterization, and electroluminescent properties of the polymers are reported in this study.