We report the photophysical behavior and photovoltaic performance of a poly(3,4-propylenedioxythiophene) (PProDOT) derivative, namely poly-[3,3-dihexyl-3,4-dihydro-2H-thieno(3,4-b)(1,4)dioxepine] (PProDOT(Hx)(2)), as an electron donor in bulk heterojunction solar cells blended with the acceptor 1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]-methanofullerene (PCBM). Devices composed of a 1:4 (w:w) ratio of PProDOT(Hx)(2)/PCBM and spin coated from chlorobenzene were characterized by measuring current-voltage characteristics under simulated Air Mass 1.5 (AM1.5) conditions as well as the spectrally resolved photocurrent (IPCE). The influence of different preparation parameters like various blend ratios, spin coating from different solvents, and changing the metal contacts was studied. It was found that the photoluminescence of the polymer is quenched by a factor greater than 100 using blends consisting of PProDOT(Hx)(2) and PCBM (3:2, w:w). Additionally, the photoactive blends were characterized by photoinduced absorption spectroscopy and the results suggest that charge transfer is occurring from PProDOT(Hx)(2) to PCBM. Results from atomic force microscopy reveal that a bicontinuous network, with domain sizes on the order of 100-200 nm, results when a 1:4 blend of PProDOT(Hx)(2)/PCBM is spin coated from chlorobenzene. (c) 2006 Elsevier B.V. All rights reserved.