We report on the near-infrared (NIR) luminescent properties of Bi 2 O 3 –GeO 2 glass. Apparent differences of NIR luminescence, decay properties and thermal stability manifest the co-existence of more than one active center in this system. The effects of Al ions introduced both unintentionally and intentionally were investigated. 27 Al NMR analysis proposes 4-fold Al coordination as dominant structure which can also provide the environment for active centers. We suggest that Al ions play a crucial role to restrain concentration quenching at higher Bi 2 O 3 concentration instead of assisting to construct Bi centers.