There has been an ongoing effort to overcome the limitations associated with the stability of hybrid organic-inorganic perovskite solar cells by using different organic agents as additives to the perovskite formulations. The functionality of organic additives has been predominantly limited to exploiting hydrogen-bonding interactions, while the relevant atomic-level binding modes remain elusive. Herein, we introduce a bifunctional supramolecular modulator, 1,2,4,5-tetrafluoro-3,6-diiodobenzene, which interacts with the surface of the triple-cation double-halide perovskite material via halogen bonding. We elucidate its binding mode using two-dimensional solid-state F-19 NMR spectroscopy in conjunction with density functional theory calculations. As a result, we demonstrate a stability enhancement of the perovskite solar cells upon supramolecular modulation, without compromising the photovoltaic performances.