Ce3+ ions were introduced into the Er3+/Yb3+-codoped TeO2-WO3-ZnO glasses, and the effect of Ce3+ on the emission properties at 1.5μm band and the upconversion luminescence of Er3+ in the glasses was investigated. With the increasing of Ce3+ concentration, the emission intensity of Er3+ at 1.5μm band increases firstly, and then decreases. The optimal doping concentration of Ce3+ is about 2.07×1020/cm3. As for the Er3+ emission at 1.5-μm band, the fluorescence lifetime decreases a little from 3.4ms to 3.0ms, while the full width at half maximum (FWHM) hardly changes with the increase of Ce3+ concentration. Due to the effective cross relaxation between Ce3+ and Er3+: Er3+(4I11/2)+Ce3+(2F5/2)→Er3+(4I13/2)+Ce3+(2F7/2), the upconversion emission intensity of Er3+ is reduced greatly. But when Ce3+-doping concentration is too high, the other cross relaxation between Ce3+ and Er3+: Er3+(4I13/2)+Ce3+(2F5/2)→Er3+(4I15/2)+Ce3+(2F7/2) happens, which depopulates the 4I13/2 level of Er3+ and results in the decrease of the emission intensity and fluorescence lifetime of Er3+ at 1.5μm band.