Control of microstructure and energetics at heterojunctions in organic semiconductors is central to achieve high light-emitting or photovoltaic device efficiency. We report the observation of an emissive exciplex formed between an electron-accepting discotic material (hexaazatrinaphthylene or HATNA-SC12) and a hole accepting conjugated polymer {poly[9,9- dioctylfluorene-co-N-(4-butylphenyl)diphenylamine] or TFB}. In contrast to polymer-polymer systems, we find here that the exciplex is strongly localized at the interface, acting as an energy bottleneck with inefficient transfer to bulk exciton states and with low yield of charge separation.