Different scanning force microscopy (SFM) techniques were employed to investigate the structure and composition of the fundamental crystal faces of prototype halogen-bonded co-crystals of long-chain perfluorocarbons. These crystals were found to show surfaces with well-defined ledges formed by intersecting crystal planes having different chemical compositions with the perfluorocarbons (PFCs) covering the largest area of the crystal as a reminiscence of the strong segregation observed in the bulk crystal structure