AbstractAn alternating copolymer with monomer units of fluorene and phenylenedivinylene was synthesized by reaction between n‐hexyl fluorene phosphonium salt and isophthalic aldehyde based on the Wittig reaction. The polymer solution in chloroform was made into a film with a very fine surface by spin‐casting on indium‐tin oxide (ITO) coated glass to fabricate a light emitting diode (LED) with an aluminum negative electrode. The optical absorption spectrum of the solid film shows a peak at 370 ran while the PL spectrum has the main peak at 560 nm with a secondary peak at 440 nm and the EL spectrum has a single peak at 560 nm showing the Stokes shift of 190 nm. The peak in the PL spectrum shifts to 420 nm with a vibronic structure at 440 nm on either dilution by chloroform or blending with polyvinylcarbazole (PVK). The emissive polymer bulk seemed to generate sites for excimers and molecular aggregates which were diminished on the dilution or blending. The peak in the EL spectrum also shifts to 440 nm on blending of 20% of the copolymer with PVK. Further dilution to 10% of the copolymer shifts the EL peak to 420 nm with the onset potential of 15 V and the highest quantum efficiency of 0.01% in this series. The concentrated channels were developed in the blends with severe phase separation to show a lower onset potential but poor quantum effic