Two types of three-component graft copolymers, in which the geometrical arrangement of the covalently-linked three polymer segments is inverse to the order of their surface energies, were synthesized, and their surface formation behavior was studied by means of contact angle and XPS measurements. Thus, poly(vinyl alcohol) (PVA)- and polyurethane (PU)-based three-component copolymers having polystyrene (PS)-block-poly(dimethylsiloxane) (PDMS) graft segments were synthesized by means of a macromonomer technique, in which PS-block-PDMS having a vinylsilane (1) or a diol (2) group at the end of the PDMS segment were prepared through the relevant end-capping reaction of a living PS-block-PDMS copolymer. The subsequent radical copolymerization of 1 with vinyl acetate, followed by the saponification of a poly(vinyl acetate), PVAc, segment produced a PVA-based copolymer having PS-block-PDMS graft segments (4). The polyaddition of 2 with diphenylmethyl diisocyanate, followed by the chain extension with butanediol produced a PU-based three-component copolymer (5). The topmost surfaces of the sample films of 4 and 5 were found to be covered with the PDMS component having the lowest surface energy, which is positioned between the PVA (or PU) and PS segments.