The charge transport in pristine poly(3-hexylthiophene) (P3HT) films and in photovoltaic blends of P3HT with [6,6]-phenyl C61 butyric acid methyl ester (PCBM) is investigated to study the influence of charge-carrier transport on photovoltaic efficiency. The field- and temperature dependence of the charge-carrier mobility in P3HT of three different regioregularities, namely, regiorandom, regioregular with medium regioregularity, and regioregular with very high regioregularity are investigated by the time-of-flight technique. While medium and very high regioregularity polymers show the typical absorption features of ordered lamellar structures of P3HT in the solid state even without previous annealing, films of regiorandom P3HT are very disordered as indicated by their broad and featureless absorption. This structural difference in the solid state coincides with partially non-dispersive transport and hole mobilities µh of around 10−4 and 10−5 cm2 V−1 s−1 for the high and medium regioregularity P3HT, respectively, and a slow and dispersive charge transport for the regiorandom P3HT. Upon blending the regioregular polymers with PCBM, the hole mobilities are typically reduced by one order of magnitude, but they do not significantly change upon additional post-spincasting annealing. Only in the case of P3HT with high regioregularity are the electron mobilities similar to the hole mobilities and the charge transport is, thus, balanced. Nonetheless, devices prepared from both materials exhibit similar power conversion efficiencies of 2.5%, indicating that very high regioregularity may not substantially improve order and charge-carrier transport in P3HT:PCBM and does not lead to significant improvements in the power-conversion efficiency of photovoltaic devices.