(HTM) of quantum dot solar cells. However, low passivation rate and poor morphology restrict the power conversion efficiency (PCE) to 11~12%. Although polymeric HTMs have been studied to address these issues, achieving both green-solvent processability and thermal stability for commercialization while retaining high PCE is necessary. Here, we synthesized a novel benzodifuran (BDF)-based HTM (asy-ranPBTBDF) showing low steric hindrance and low planarity compared to those of a typical benzodithiophene (BDT)-based HTM (asy-ranPBTBDT). With these benefits, the asy-ranPBTBDF-based CQD-SC showed enhanced open-circuit voltage (VOC) (0.65 V) and PCE (13.29%) compared to those of the asy-ranPBTBDT-based device (0.63 V and 12.22%) in toxic processes with chlorobenzene.