摘要： Two-dimensional (2D) perovskites with natural multi-quantum-well structure have been reported to offer better stability compared to 3D perovskites. However, the understanding of the exciton separation and transport mechanism in 2D perovskite as well as developing more efficient organic spacers remain considerable challenges as the 2D perovskite exhibit large exciton binding energy due to quantum confinement. Here, a class of multiple-ring aromatic ammoniums, 1-naphthalenemethylammonium (NpMA) and 9-anthracenemethylammonium (AnMA), were developed as spacers for 2D Ruddlesden-Popper (RP) perovskite solar cells (PSCs). In addition to significantly enhanced stability, the device based on (NpMA)2(MA)n-1PbnI3n+1 (average n = 4) exhibits a champion efficiency of 17.25% and a high open circuit voltage of 1.24 V. The outstanding photovoltaic performance could be ascribed to the ultrafast exciton migration (within 7 ps) from 2D phases to 3D-like phases, which were confirmed by charge carrier dynamics results, leading to efficient exciton separation, charge transportation and collection. This work facilitates understanding the working mechanism of 2D PSCs deeply and offers an efficient way to further boosting their efficiency and stability by developing multiple-ring aromatic spacers.