Highly regioregular poly[3-(4-octylphenylthiophene)] (POPT) was prepared to study the influence of phenyl groups as substituents on photovoltaic and thermal properties with respect to poly(3-hexylthiophene) (P3HT). The UV-visible absorption spectra of spin-coated films of POPTexhibited an extended absorption towards the near infrared. Differential scanning calorimetry showed the poor tendency of POPT to crystallise. In order to retain the extension in absorption and increase crystallinity, poly(3-hexylthiophene)-block-poly(3-tolylthiophene) (P3HT-b-P3TT) samples with varying ratios of P3HT and P3TT were prepared. Thermal fractionation by successive self-nucleation and annealing indicated that crystallites of P3HT were influenced by the P3TT block within the copolymers. Thermogravimetric analysis showed that thermal stabilities increased with increasing fractions of phenyl groups. Photovoltaic results of these materials blended with [6,6]-phenyl C-61 butyric acid methyl ester (PCBM) are presented and discussed. (c) 2007 Elsevier B.V. All rights reserved.