The surface and bottom compositions of poly(2-ethylhexyl acrylate) (P2EHA)/poly-(vinylidene fluoride-co-hexafluoro acetone) [P(VDF-HFA)] blends were investigated by XPS analysis. In these blends, the enriched P(VDF-HFA) layer was observed from the top surface to a few nm depth, while the P2EHA component segregated at the bottom (the surface in contact with release liner). The probe tack values of the bottom side were remarkably larger than those of the surface side for the P2EHA/P(VDF-HFA) blends because the characteristic segregation structure was formed. We expected that the P2EHA/P(VDF-HFA) blends could be utilized as a non-backing pressure sensitive adhesive (PSA) tape. The effects of the film thickness of the blends and the molecular weights of P2EHA on the segregation structure were also examined. We thought that segregation behavior found in P2EHA/P(VDF-HFA) blends was caused by several factors, such as surface tension, miscibility, density, and rate of solvent casting.