X-ray absorption near edge structure (XANES) spectra is used as a probe of surface structure of α-Fe 2O 3 nanocrystal, prepared by sol-gel method. We present O K-edge XANES of α-Fe 2O 3 in nanocrystal and bulk by total electron yield at the photoemission station of Beijing Synchrotron Radiation Facility. The spectrum of α-Fe 2O 3 shows a splitting of the pre-edge structure, which is interpreted as two subsets of Fe 3d t 2g and e g orbitals in oxygen octahedral (O h) crystal field, and is also sensitive to long-range order effects. However, no distinguishable splitting of the pre-edge peak of nanocrystal α-Fe 2O 3 is observed. This suggests that there exists the distorted octahedral coordination around Fe sites and also the long-range disorder due to the surface as compared with bulk α-Fe 2O 3.