Notwithstanding the numerous density functional studies on the chemically induced transformation of multilayer graphene into a diamond-like film carried out to date, a comprehensive convincing experimental proof of such a conversion is still lacking. We show that the fluorination of graphene sheets in Bernal (AB)-stacked bilayer graphene grown by chemical vapour deposition on a single-crystal CuNi(111) surface triggers the formation of interlayer carbon–carbon bonds, resulting in a fluorinated diamond monolayer (‘F-diamane’). Induced by fluorine chemisorption, the phase transition from (AB)-stacked bilayer graphene to single-layer diamond was studied and verified by X-ray photoelectron, UV photoelectron, Raman, UV-Vis and electron energy loss spectroscopies, transmission electron microscopy and density functional theory calculations.