The Er3+/Yb3+ co-doped TeO2–Nb2O5–Li2O glass is prepared by conventional melting method and its upconversion spectra are measured. The intense green upconversion luminescence upon excitation with a 976 nm laser diode is observed with the naked eyes. The dependence of luminescence intensity on the ratio of Yb3+/Er3+ is discussed in detail and the relationship between the ratio of green luminescence intensity to red luminescence intensity and the ratio of Yb3+/Er3+ is also studied. The luminescence intensity increases with the ratio of Yb3+/Er3+increasing. The ratio of Yb3+/Er3+ plays a more important role than the concentration of Er3+ in determining the upconversion luminescence intensity. The ratio of green luminescence intensity to red luminescence intensity reaches a maximum when ratio of Yb3+/Er3+ is 3. Thus the glass could be one of the potential candidates for LD pumping solid-state lasers.