Photovoltaic devices based on poly-2,5-dioctyl-4,4"-terphenylenecyanovinylene (J-domain) and 4-aza-4-(4'-(poly-2,5'-dioctyl-4,4"-terphenylene-1-cyanovinylene-2-yl)biphen-4-yl)-8,12-dioxa-4,8,12,12c-tetrahydrodibenzo[ed,mn]pyrenium tetrafluoroborate (JA-assembly) were prepared using indiumtinoxide (ITO) as the transparent electrode and aluminium as the second electrode. While the photovoltaic response of the J-domain exhibited low short circuit currents of -0.1 nA cm(-2), the corresponding short circuit current of the JA-assembly was observed to be + 10 nA cm(-2). The 100-fold increase in magnitude was related to the known energy transfer from the J-domain to the A-domain in the JA-assembly, and the inversion of the sign of the photovoltaic response that implies that the electrodes have a reversed polarity was explained on the basis of the positions of the energy levels and involves the action of the A-domain as a blocking layer and a light operated charge pump that efficiently transfers electrons to the ITO electrode. (C) 2003 Elsevier B.V. All rights reserved.