<title>Abstract</title>Interhalogen compounds (IHCs) are extremely reactive molecules used for halogenation, catalyst, selective etchant, and surface modification. Most of the IHCs are unstable at room temperature especially for the iodine-monofluoride (IF) whose structure is still unknown. Here we demonstrate an unambiguous observation of two-dimensional (2D) IF bilayer grown on the surface of WSe₂ by using scanning transmission electron microscopy and electron energy loss spectroscopy. The bilayer IF shows a clear hexagonal lattice and robust epitaxial relationship with the WSe₂ substrate. Despite the IF is known to sublimate at −14 °C and has never found as a solid form in the ambient condition, but surprisingly it is found stabilized on a suitable substrate and the stabilized structure is supported by a density functional theory. This 2D form of IHC is actually a byproduct during a chemical vapor deposition growth of WSe₂ in the presence of alkali metal halides as a growth promoter and requires immediate surface passivation to sustain. This work points out a great possibility to produce 2D structures that are unexpected to be crystallized or cannot be obtained by a simple exfoliation but can be grown only on a certain substrate.