Luminescence from Bi and Bi/Er doped aluminum calcium germanate glasses were investigated. The glasses were prepared by conventional melting-quenching technique. The near infrared luminescence of Bi-doped calcium aluminum germinate glasses can be divided into two Gaussian peaks which are located at 1 265 and 1 420 nm separately. The X-ray photoelectron spectroscopy spectrum indicates the valence state of Bi ions in the calcium aluminum germinate glasses is the mixed. Bi3+ ions could be reduced to low valence states bismuth ions. The experiments support the assumption that the near-infrared luminescence is connected with a low valence state of Bi, may be Bi+. Er3+ was introduced to adjust the 1420 nm band of Bi-related fluorescence. With the increment of Er3+ concentration, near-infrared fluorescence relative intensity of Bi ions is decreasing, which implies the energy transfer from Bi ions to Er3+.