We report the fused ring electron acceptor (FREA)-perovskite hybrid as a promising platform to fabricate organic-inorganic hybrid solar cells with simple preparation, high efficiency, and good stability. The FREA-perovskite hybrid films exhibit larger grain sizes and stronger crystallinity than the pristine perovskite films. Moreover, the FREA molecules can form coordination bonding with undercoordinated Pb atoms and passivate the trap states in the perovskite films. Time-resolved photoluminescence and transient absorption measurements reveal that FREA facilitates efficient electron extraction and collection. Transient photocurrent and photovoltage measurements suggest faster charge transfer and reduced charge recombination in solar cells based on FREA-perovskite hybrid films. Consequently, solar cells based on FREA-perovskite hybrid films yield a champion efficiency of 21.7% with enhanced stability, which is higher than that of the control devices based on pristine perovskite films (19.6%).