New copoly(arylether)s containing substituted terphenyl, quinquephenyl, fluorene and anthracene moieties with aromatic 1,3,4-oxadiazole units were prepared and the resulting copolymers are soluble in common organic solvents. Investigation of their optical properties revealed that they emit blue and yellow light. Moreover, their photovoltaic response was studied in blends with poly(3-hexylthiophene) (P3HT) as the electron donor. Despite the low power conversion efficiencies it was shown that photo-induced electron transfer does take place and the performances are higher than a single layer P3HT device. In addition, an anthracene-fluorene-oxadiazole main chain copolymer (PAFOXD) was also examined in a single layer photovoltaic device and gave one of the highest reported open-circuit voltage (V c) values in the literature (0.89 V). Finally, a detailed morphological study of the blends and the PAFOXD surface using the atomic force microscopy (AFM) technique, revealed the effect of solvent selection to the preparation of thin films exhibiting the desired performance characteristics. (c) 2005 Elsevier Ltd. All rights reserved.