Abstract Following the previous demonstration of electroluminescence emission from polyvinylcarbazole (PVCz) films having caesium cathodes, the possibility of using less chemically reactive higher work function cathodes was studied. It is shown that this can in principle be accomplished by the use of suitable electron-accepting additives in the PVCz films and a range of cyanobenzene molecules was used for this purpose. The fluorescent properties of the exciplexes and exterplexes inevitably formed between the cyanobenzene acceptors and the carbazole donor groups of the PVCz were investigated in order to determine the most suitable additives. Acceptor anions and carbazole cations in PVCz films were observed spectroscopically at low temperatures as was their recombination luminescence on subsequent warming. Finally, electroluminescence was observed from PVCz films containing cyanobenzene additives and using cathodes of barium or calcium.