Journal ArticleWe present time-resolved photoluminescence measurements on a range of poly- and oligofluorenes with different molecular weights in both dilute solution and thin films. The commonly observed parasitic broad green emission band, which has previously been attributed to an excimer, is identified in all solution and film samples and assigned to an on-chain emissive defect. By comparison of the luminescence decay in the solid state at different temperatures it is shown that, at room temperature, intramolecular relaxation is faster in these polyphenylenes than intermolecular exciton diffusion