Hole collection and transport are crucial physical processes in bulk-heterojunction (BHJ) solar cells, which represent major bottlenecks due to their limitations in power conversion efficiency (PCE). Hence, a more efficient alternative is needed to accept and transport holes to the collection electrode in BHJ solar cells. Here, we bring both electron and hole collection centres close to the point of exciton generation by infiltrating P3HT poly(3-hexylthiophene):PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) blend into a highly porous interconnected p-type NiO-nanoparticle (NiO-np) network, through solvent-assisted grafting. In this study, a hybrid polymer solar cell is demonstrated with a P3HT:PCBM:NiO-np triple-heterojunction active layer which showed greatly improved rectification behaviour, long electron lifetime and generated higher PCE of 4% under AM 1.5 solar illumination with a 75% increase in PCE with respect to the P3HT:PCBM device. The optimum NiO-np amount and active-layer thickness were found to be 2% and 250 nm, respectively.