We report the phase-separation and the optoelectronic properties of an alternating poly(p-phenylene vinylene)-based copolymer, to which poly(ethylene oxide), PEO, and or lithium triflate are added. The alternating units of this copolymer (DB-BTEM-PPV) are 2,3-dibutoxy-1,4-phenylene vinylene, and 2,5-bis(triethoxymethoxy)-1,4-phenylene vinylene, a moiety containing side groups allowing ion solvation and transport. Upon addition of the ion-transporting polymer PEO to DB-BTEM-PPV blended with lithium triflate, we have found a sizeable efficiency increase (from 0.9 to 1.5 cd/A), with a concomitant increase of the response time. We propose that this is due to solvation and complexation of lithium triflate by the PEO, which simultaneously reduces the quenching of photoluminescence (and electroluminescence) efficiency by the ionic charge, and the effectiveness of formation of highly doped, low-barrier, polymer/electrode interfaces. We discuss charge transport and injection in the copolymer and in the blend with reference to the diodes characteristics, and to the phase separation of PEO, which we investigated with atomic force microscopy. © 1999 American Institute of Physics.