We report the fabrication of polymer electroluminescent devices on doped silicon substrates. An electron‐injecting aluminum electrode is thermally evaporated onto the silicon substrate, and a layer of a high electron affinity conjugated polymer, poly(cyanoterephthalylidene), CN‐PPV, is then spin coated onto this. A hole‐transporting layer of poly(p‐phenylene vinylene), PPV, is formed on top of the CN‐PPV layer by thermal conversion of a spin‐coated layer of the sulphonium precursor polymer. Finally, a transparent hole‐injecting top electrode of indium‐tin oxide is formed by rf sputtering. These devices show efficient red electroluminescence, with emission from the CN‐PPV layer. © 1994 American Institute of Physics.