Blended regio-regular P3HT–ZnO nanoparticles are a hybrid material developed as an active layer for hybrid solar cells. The study of the hopping mechanisms and diffusion rates of regio-regular P3HT–ZnO nanoparticles is significant for obtaining intrinsic charge transport properties that provide helpful information for preparing high-performance solar cells. The temperature dependences of the parallel and perpendicular diffusion rates in regio-regular P3HT–ZnO nanoparticles determined from muon spin relaxation measurements were investigated by applying various longitudinal fields. We investigated the effect of light irradiation on the diffusion rates in regio-regular P3HT–ZnO nanoparticles. We found that with increasing temperature, the parallel diffusion rate decreased, while the perpendicular diffusion rate increased. The ratio of the parallel to perpendicular diffusion rate (D‖/D⊥) can be used to indicate the dominant charge carrier hopping mechanism. Without light irradiation, perpendicular diffusion dominates the charge carrier hopping, starting at 25 K, with a ratio of 1.70×104, whereas with light irradiation, the perpendicular diffusion of the charge carrier starts to dominate at the temperature of 10 K, with a ratio of 2.40×104. It is indicated that the additional energy from light irradiation affects the diffusion, especially the charge diffusion in the perpendicular direction.