Pulse radiolysis has been used to study the positively charged state of isolated chains of poly[9,9-di(ethylhexyl)fluorene] in chloroform solution. This is found to have an absorption maximum at 560 nm and a weaker band around 420 nm. Intermolecular electron transfer is observed from the aromatic amine tri(p-tolylamine) to this species. With the corresponding polyfluorene derivative end-capped by an arylamine, intramolecular transfer of electrons from the triphenylamine end-cap to the positively charged polyfluorene chain is found on timescales faster than the detection time of the system (ca. 500 ns). (C) 2003 Elsevier B.V. All rights reserved.