We investigated nature of the orientation in the topmost layers of F + -irradiated graphite using polarizationdependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, incorporating partial electron-yield (PEY) detection and photon-stimulated ion desorption (PSID) techniques. The fluorine K-edge NEXAFS spectra conducted in PEY mode showed no significant dependence on polarization angles. In contrast, NEXAFS spectra recorded in F + ion yield mode showed enhanced yields at a feature of ∼689.4 eV, assigned as a s * (C-F) state relevant to C-F sites: furthermore, the yields depended on polarization angles. The F + ion yields at the feature are larger in normal incidence than in grazing incidence, suggesting that the C-F bonds prefer a relatively downward tilt at the topmost layer, while being randomly directed at deeper regions. We conclude that the difference in the orientation structures between the surface and the bulk is reflected in the NEXAFS spectra recorded in the two different detection modes. It was also found that H + -and F 2+ -PSID NEXAFS spectra are helpful in understanding the desorption mechanisms, and thus in analysing NEXAFS data.