From observations of the atomic and friction force microscopies, it has been found that the mixed monolayers of the comb polymer having the fluorocarbon side-chains and the hydrogenated amphiphile, exhibit a characteristic phase separation behavior at the micro- and mesoscopic resolutions. The regularity for molecular orientation in the mixed film was compared with that in the pure monolayer of the fluorinated comb polymer by using polarized NEXAFS spectroscopy.