Macroporous -Al2O3 is synthesized by polyacrylamide gel technique. X-ray diffractor combined with a photoluminescence spectrophotometer is used to investigate the formation of Al2O3 phase and the light emission properties of xerogel sintered at different temperatures. It is demonstrated that high-purity -Al2O3 can be obtained at a sintering temperature of 1150 ℃. Scanning electron microscopy images reveal that the synthesized -Al2O3 has a monolithic structure. Photoluminescence spectra show that a major emission band around 365 nm and a weaker side band around 330 nm are observed when the excitation wavelength is 228 nm. The pore-formation and luminescence mechanisms of porous alumina are discussed based on the experimental results.