CsPbI 3 quantum dots (QDs) are of great interest in new-generation photovoltaics (PVs) due to their excellent optoelectronic properties. The long and insulative ligands protect their phase stability and enable superior photoluminescence quantum yield, however, limiting charge transportation and extraction in PV devices. In this work, we use a fullerene derivative with the carboxylic anchor group ([SAM]C60) as the semiconductor ligand and build the type II heterojunction system of CsPbI 3 QDs and [SAM]C60 molecules. We find their combination enables obvious exciton dislocation and highly efficient photogenerated charge extraction. After the introduction of [SAM]C 60 , the exciton-binding energy of CsPbI 3 decreases from 30 meV to 7 meV and the fluorescence emission mechanism also exhibits obvious changes. Transient absorption spectroscopy visualizes a ~5 ps electron extraction rate in this system. The findings gained here may guide the development of perovskite QD devices.