Thermal crosslinking using a suitable radical initiator simultaneously improves electrical conductivity in the semiconducting polymer poly(3-hexylthiophene) and makes the material insoluble. Crosslinked polythiophene shows as much as a fivefold increase in hole conductivity across the film thickness without any shift in spectral light absorption. Grazing incidence x-ray diffraction reveals more in-plane polymer lamellae stacking with only a small decrease in film crystallinity. Improved transverse conductivity increases the performance of model planar solar cells by threefold, from 0.07% to 0.2%. The ability to render polythiophene insoluble without disrupting film structural order enables fabrication pathways to more complex device architectures. (C) 2009 American Institute of Physics. [doi:10.1063/1.3254685]