The electronic structure and optical properties of bulk, micro-sized, and nano-sized α-Al2O3 (wafer, microparticles (MPs), nanowires (NWs), and nanotubes (NTs)) have been investigated using X-ray absorption near-edge structures (XANES) and X-ray excited optical luminescence (XEOL). XANES results show that the wafer, MPs, and NTs have characteristic features of α-Al2O3. The NWs have a core∕shell structure with a single crystalline α-Al2O3 core surrounded by an amorphous shell, which is consistent with transmission electron microscopy result. It is found that some Al(3+) in the shell and core∕shell interface of the NWs as well as the surface of the NTs were reduced to Al(2+) or Al(1+) during the growth process. XEOL results show that the wafer and MPs have a broad emission at 325 nm and a sharp emission at 694 nm, which are attributed to F(+) center and Cr(3+) impurities, respectively. The NWs exhibit an intense emission at 404 nm that comes from F center, while the NTs show relatively weak luminescence at 325, 433, and 694 nm, which are attributed to F(+) center, F center, and Cr(3+) impurities, respectively. The O K-edge XEOL confirms that the emissions of α-Al2O3 in the range of 250-550 nm are related to the oxygen site. Furthermore, on the basis of XEOL and photoluminescence yield, the strong luminescence of the NWs (404 nm) is related to the Al(2+) or Al(1+) in the shell and core∕shell interface, while the luminescence of the NTs at 325 and 433 nm are related to the bulk and the Al(2+) or Al(1+) on the surface, respectively.