High-efficiency Pb−Sn narrow-bandgap perovskite solar cells (PSCs) heavily rely on PEDOT:PSS as the hole-transport layer (HTL) owing to its excellent electrical conductivity, dopant-free nature, and facile solution processability. However, the shallow work function (W F) of PEDOT:PSS consequently results in severe minority carrier recombination at the perovskite/HTL interface. Here, we tackle this issue by an in situ interface engineering strategy using a new molecule called 2-fluoro benzylammonium iodide (FBI) that suppresses nonradiative recombination near the Pb−Sn perovskite (FA 0.6 MA 0.4 Pb 0.4 Sn 0.6 I 3)/HTL bottom interface. The W F of PEDOT:PSS increases by 0.1 eV with FBI modification, resulting in Pb−Sn PSCs with 20.5% efficiency and an impressive V OC of 0.843 V. Finally, we have successfully transferred our in situ buried interface modification strategy to fabricate blade-coated FA 0.6 MA 0.4 Pb 0.4 Sn 0.6 I 3 PSCs with 18.3% efficiency and an exceptionally high V OC of 0.845 V.