Bi/Yb3+ co-doped germanate glasses were prepared by conventional melting-quenching technique. Near infrared (NIR) luminescence properties in Bi/Yb3+ co-doped germanate glasses were investigated by the absorption spectrum, NIR luminescence spectra, and fluorescence lifetime measurement. NIR luminescence of both Yb3+ and Bi ions was observed simultaneously, either under 980 or 808 nm excitation LD. The results show that ET process existed between Bi-related NIR emission centre and Yb3+ ions. With the increasing in Yb3+ ions concentration, both ET efficiency from Yb3+ ions to Bi ion and optical basicity of glass matrix are increased. The competitive effects of enhancing by the ET process and weakening by optical basicity on NIR luminescence properties of Bi ions were investigated.