In this paper, the adhesion characteristics between a fused silica without or with an anti-sticking layer and a thermoplastic polymer film used in thermal NIL were investigated experimentally in order to identify the release performance of the anti-sticking layer. The anti-sticking layers were derived from fluoroalkylsilanes, (1H, 1H, 2H, 2H-perfluorooctyl)trichlorosilane (F13-OTS) and (3, 3, 3-trifluoropropyl)trichlorosilane (FPTS), and coated on the silica surface in vapor phase. The commercial polymers, mr-I 7020 and 8020 (micro resist technology, GmbH), for thermal NIL were spin-coated on Si substrate with a rectangular island which was fabricated by conventional microfabrication process to achieve small contact area and easy alignment of flat contact surfaces. Experimental conditions were similar to the process conditions of thermal NIL. When the polymer film on the island was separated from the silica surface after imprint process, the adhesion force between the silica surface and the polym film was measured and the surfaces of the silica and the polymer film after the separation were observed. As a result, the anti-sticking layers remarkably reduced the adhesion force and the surface damage of polymer film and the chain length of silane affects the adhesion characteristics. The anti-sticking layers derived from FPTS and F13-OTS reduced the adhesion force per unit area to 38% and 16% of the silica surfaces without an anti-sticking layer, respectively. The anti-sticking layer derived from F13-OTS was more effective to reduce the adhesion, while both of the anti-sticking layers prevented the surface damages of the polymer film. Finally, it is also found that the adhesion characteristics of mr-I 7020 and mr-I 8020 polymer films were similar with each other.