Core–mantle nanohybrids were prepared via grafting the multi-walled carbon nanotubes (MWCNTs) with polyaniline (PANI). Core–mantle–shell supramolecules were then designed by crystallization of poly(3-hexylthiophene) (P3HT) and poly[benzodithiophene-bis(decyltetradecyl-thien) naphthothiadiazole] (PBDT-DTNT) conductive polymers onto core (CNT)– mantle (PANI) nanostructures. Supramolecules were thoroughly investigated and applied in active layers of P3HT:phenyl�C71-butyric acid methyl ester (PC71BM) solar cells. Efcacies of 5.71% and 6.02% were acquired for photovoltaics based on nanostructures having PBDT-DTNT and P3HT shells, respectively. Diameters of core(CNT)–mantle(PANI), core(CNT)– mantle(PANI)–shell(P3HT), and core(CNT)–mantle(PANI)–shell(PBDT-DTNT) supramolecules ranged in 75–90 nm, 145– 160 nm, and 120–130 nm, respectively. The highest efciency (=6.02%) was achieved for P3HT:PC71BM:CNT-graft-PANI/ P3HT systems without any post-treatment (13.42 mA/cm2 , 0.68 V, and 66%). Charge mobilities were also very high for corresponding electron-only (µe =9.8×10−3 cm2 /V s) and hole-only (µh=5.0×10−3 cm2 /V s) devices. PANI mantle may act as both acceptor and donor in core–mantle–shell supramolecules. Core(CNT)–mantle(PANI)–shell(PBDT-DTNT) nano�structures also elevated photovoltaic efciency up to 5.71% (13.12 mA/cm2 , 0.67 V, 65%, 4.7×10−3 cm2 /V s, and 9.0×10−3 cm2 /V s). Results acquired for core(CNT)–mantle(PANI)–shell(P3HT)-based systems were somehow higher than those recorded for core(CNT)–mantle(PANI)–shell(PBDT-DTNT)-based ones. It could be assigned to consistency of P3HT shells and P3HT host chains in bulk of P3HT:PC71BM active layer. P3HT backbones owing to their simpler chemical structures were also capable of arranging more ordered shells, leading to larger charge mobilities and currents.