Insertion effects of multiwalled carbon nanotubes (MWNTs) at different loads in the regioregular poly(3-hexylthiophene) (RR-P3HT) electroactive polymer are investigated with transmission electron microscopy (TEM), X-ray diffraction, infrared and optical absorption, photoluminescence (PL) and photoconductivity techniques. MWNTs in composites quench the deep red emission of P3HT. They also act as inhibitors of polymer aggregates favoring shorter conjugated segments during composite synthesis and the formation of a charge-transfer complex at the P3HT/MWNT interface through delocalization of π electrons along the conjugated segments. Under photoexcitation, a significant fraction of excitons dissociates non radiatively with charge hopping towards the MWNTs network and triggers an augmentation of photoconductivity.