Many studies have shown that the severe photoluminescence quantum yield (PLQY) loss at the interface between the perovskite and electron transport layer (ETL) is the main cause of voltage loss in inverted perovskite solar cells (p-i-n PSCs). However, currently there are no effective in situ passivation techniques to minimize this nonradiative recombination. Here, the fluorinated pseudohalide ionic liquid (FPH-IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIMTFSI) is introduced into the perovskite precursor formulation. EMIMTFSI can change the dielectric environment and energy-level arrangement of the perovskite by accumulating on the top surface and spontaneously forming dipoles. As a result, the excitonic binding energy (Eb) and nonradiative recombination loss are significantly reduced. At the same time, TFSI- reduces the formation energy of vacancy defects and stabilizes the perovskite phase by forming N-H⋯F hydrogen bonds between FA+ and the C-F bond in EMIMTFSI. Finally, the EMIMTFSI-modified p-i-n PSCs achieve an excellent efficiency of 24.81% with an impressive open-circuit voltage of 1.191 V for a 1.57 eV low-bandgap perovskite. In addition, the modified devices can maintain more than 95% PCE after continuous thermal aging at 85 °C for 500 h or illumination at the maximum power point for 800 h. This work provides a new idea for minimizing the non-radiative recombination losses in p-i-n PSCs.