The surface tensions (gamma) of poly(ethyl acrylate) (PEA)/poly(vinylidene fluoride-co-hexafluoro acetone) (P(VDF-HFA)) blends were estimated by means of the contact angles with organic liquids Theta and bulk pressure-volume-temperature (PVT) properties. Two methods of estimation provided different gamma values related to the surface segregation behaviour and the rearrangement. The change of gamma against volume fraction of P(VDF-HFA) for PEA/P(VDF-HFA) blends was calculated using thermodynamic theory on gamma of miscible polymer blends presented by Kammer. Finally, the surface segregation behaviour of P(VDF-HFA) component could also be expressed with the experimental data of gamma and the Kammer theory.