Surface morphology of monolayers related to solid-state structure for methacrylate comb copolymers having fluorocarbon and hydrocarbon side-chains was investigated by X-ray diffraction (XRD), differential scanning calorimetry, and atomic force microscopy (AFM). From the XRD profiles, two kinds of short spacing peaks were confirmed at 5.0 and 4.2 angstrom, which assigned the sub-cells for both side-chains. Furthermore, two kinds of endothermic peaks, which corresponded to melting peaks of the both side-chain crystals, appeared in the thermograms. From the AFM observation, it was found that there were hydrogenated domains at a few hundred nanometer diameter in their monolayers, whereas corresponding acrylate copolymer monolayers form the phase-separated structure at 10-30 nm order scales.