We have investigated the enhancement of light absorption and carrier transport of poly(3-hexylthiophene) (P3HT) resulted from doping with multi-wall carbon nanotubes (MWNTs). The MWNTs were acid washed first, and then incorporated into P3HT homogenously. The MWNTs make P3HT unfolded with more alignment and thus increase light absorption as shown by the studies of AFM and UV–vis spectroscopy. The KFM data provides useful information to differentiate the work function of the MWNTs from P3HT and further show improved hole transporting behaviors. Based upon these results, the 0.01 wt% MWNTs doped P3HT/PCBM photovoltaic device shows an increase of 29% power conversion efficiency.