The study of nanoimprint lithography (NIL) has attracted much attention for many industrial fields because it is a promising method to fabricate various nanostructures with a low cost and a high throughput. In the process of NIL, the mold is usually coated with an antisticking layer to avoid resist adhesion. As an antisticking layer of nanoimprint mold, the fluorinated self-assemble monolayer (F-SAM) is used, for example. The evaluation of the F-SAM with different chain length is one of the critical issues in NIL. In this study, four kinds of F-SAMs with different chain length were evaluated using the photoelectron and the near edge X-ray absorption fine structure (NEXAFS) spectroscopies. Four kinds of F-SAMs were prepared from a precursor [CF 3 (CF 2) n (CH 2) 2 Si(OCH 3) 3 ; n = 0, 3, 5, and 7] as denoted FAS-3, 9, 13, and 17, respectively. All photoelectron and NEXAFS measurements were performed on a BL7B end station at the NewSUBARU facility, University of Hyogo. The photoelectron spectra were measured using the Mg Kα line at the total energy resolutions of about 0.7 eV for the C 1s core-level region. NEXAFS spectra were measured using the synchrotron radiation by the total electron yield method. The total energy resolution was about 0.5 eV. In Figure 1, the photoelectron spectra of the C 1s core-level region in four kinds of F-SAMs with different chain length are plotted. In the photoelectron spectra of the C 1s core-level, three peaks at 292, 286, and 284.5 eV were observed in FAS-3 although four peaks at 293, 291, 286, and 284.5 eV were observed in FAS-9, 13, and 17. With increasing the chain length, the intensity of the peak at 291 eV increased while the intensity of the peaks at 293 and 286 eV did not change. From the chemical compositions of four kinds of F-SAMs with different chain length, these peaks at 293, 291, 286, and 284.5 eV were assigned to the CF 3 , CF 2 , CH, and CC components, respectively. In FAS-3, the CF 3 component shifted to lower binding energy side by 1 eV since there is no CF 2 chain. Figure 2 shows the NEXAFS spectra in four kinds of F-SAMs with different chain length. Several peaks were observed at 285, 290, 292, 295, and 299 eV. The intensity of the peaks at 292 and 299 eV increased with increasing the chain length. On the other hand, the intensity of the peaks at 285, 290, and 295 eV did not change with increasing the chain length. The peaks at 292 and 299 eV were assigned to the σ*(C-F) transition from C 1s core-level. On the other hand, these peaks at 285, 290, and 295 eV were assigned to the π*(C-C) and σ*(C-H), π*(C=O) and σ*(C-H), and σ*(C-C) components, respectively. When the incidence angle of the linearly polarized synchrotron radiation to the sample surface increased, the intensity of the peaks at 292 and 299 eV increased. This indicates that the σ*(C-F) orbital is parallel to the surface and that the CF 2 chain in F-SAMs is perpendicular to the surface. Intensity (arb.units) 295 290 285 280 Binding energy (eV)