We investigated the molecular orientation of organized molecular films with regard to solid-state structures for newly synthesized comb copolymers with 2-vinyl-4,6-diamino- 1,3,5-triazine (VDAT) by surface pressure-area (pi-A) isotherms, in-plane and out-of-plane X-ray diffraction (XRD), atomic force microscopy (AFM), and polarized near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Since VDAT has adsorption ability to an adenine-thymine base pair of a DNA molecule, control of orientation for VDAT units in monolayers is possible to form surface patterning of biomolecules and construct candidates of new biochip materials. In the bulk state, hydrogenated and fluorinated comb copolymers containing VDAT form side-chain crystals for a two-dimensional lattice spacing of 4.2 and 5.0 angstrom, respectively. From the results of the differential scanning calorimetric (DSC) measurements, sharp-shaped melting peaks appear on the relatively lower temperature side of the thermograms. This result supports the formation of side-chain crystals in the synthesized comb copolymers. These monolayers of copolymers on the water surface were extremely condensed, except for the VDAT:OA = 5:1 copolymer. From the in-plane XRD measurement of multilayers on solids, changes in the two-dimensional lattice structure of fluorinated comb copolymer films containing VDAT units, as opposed to their bulk state, were confirmed. It seems that these structural changes are caused by the stronger pi-pi interaction between the s-triazine rings rather than the van der Waals interaction between fluorocarbons. Polarized NEXAFS spectroscopy showed highly ordered orientation of s-triazine groups in the films based on the incident angle dependency of C and Nls-pi*(C=N) transitions with synchrotron radiation. These experimental findings relate to well-ordered arrangement of functional groups supporting the side-chain rearrangement caused by the pi-pi interaction between the s-triazine rings.