Layer structures and the molecular packing in the two-dimensional lattice were studied by using the in-plane X-ray diffractions in addition to the conventional small-angle XRD, and the polarized near-edge X-ray absorption fine structure (NEXAFS) spectra for the multilayers of fluorinated amphiphiles with vinyl groups and their comb-polymers containing fluorocarbons as the side-chains. These molecular lattices were significantly different from the bulk crystals due to the film compression.. and NEXAFS results show that the molecular arrangements of the fluorocarbon sidechains were strongly influenced by atoms at the omega -position of the fluorocarbon-chains.