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A tunable luminescence from red to blue in Eu-doped mesoporous AlPO4 glass is achieved by adjusting the annealing temperature. With increasing annealing temperature, the increased Eu3 ions reduction changes the luminescence of the obtained glass. The abnormal reduction of Eu3 to Eu2 occurs in AlPO4 mesoporous glass at relative low annealed temperatures from 600 to 800 oC in air. The presence of Eu2 ions, which are reduced from Eu3 by hole-electron pairs, is revealed by XPS spectra. Our results indicate the mesoporous AlPO4 glass is a suitable matrix to incorporate Eu ions as the tunable luminescent light sources or LEDs.