Abstract Photoluminescence and electroluminescence of PVK films doped with fac-[ClRe(CO) 3(bpy)], bpy = 2,2′-bipyridine, are investigated. Photoluminescence spectra of spin-coated PVK films ( λ exc = 290 nm) exhibit a broad band centered at 405 nm. As the concentration of dopant increases, the polymer emission is quenched and a band at 555 nm appears (isosbestic point at 475 nm). In OLEDs with ITO/PEDOT:PSS/PVK/butylPBD/Al architecture doped with fac-[ClRe(CO) 3(bpy)], the polymer host emission is completely quenched even at the lowest concentration of dopant. The electroluminescence spectra of the devices show that there is an efficient energy transfer from the host to the dopant, which exhibits a very intense emission at 580 nm.