AbstractThe non‐radiative recombination at the interfaces of perovskite solar cells (PSCs) is a crucial issue that limits the efficiency and stability of the devices. State‐of‐the‐art surface passivation strategies usually utilize alkyl ammonium halides to suppress the non‐radiative recombination of PSCs, but their high surface reactivity leads to the transformation into 2D perovskites under working conditions, limiting the passivation effect and the charge transport of PSCs. Herein, a non‐halide ionic salt 1‐naphthylmethylammonium formate (NMACOOH) is synthesized for surface passivation of perovskite films. In contrast to the traditional 1‐naphthylmethylammonium iodide, NMACOOH treatment hinders the formation of 2D perovskite and forms a thermally stable PbI2‐NMACOOH adduct on the perovskite surface. Surface characterization reveals that NMA+ can passivate the cation vacancies of the 3D perovskite while HCOO− passivates the metallic Pb0 and halide‐vacancy defects. Therefore, the non‐radiative recombination of PSCs is dramatically suppressed and a high open‐circuit voltage of 1.19 V is obtained. Finally, PSCs with high efficiency of 24.75% and improved long‐term stability (98% of the initial efficiency after 1800‐h storage) are obtained. Moreover, the NMACOOH‐passivated devices also show robust operational stability, retaining 83% of the initial efficiency after working for 658 h under continuous one‐sun illumination.