Energy transfer processes of Tm3+ singly doped and Tm3+/Ho3+-codoped TeO2-WO3-ZnO glass have been investigated under excitation of 808 nm diode laser and the involved mechanisms are discussed. The microscopic parameters and critical radii are calculated by using Dexter model and their characteristics are analyzed. The Inokuti-Hirayama model improved by Vila et al. is utilized to fit the fluorescence decay curves of Tm3+. The results indicate that there are not only Inokuti-Hirayama-type solution but also localized interaction solution in the energy transfer processes of Tm3+ and Ho3+. Furthermore, the contribution of the localized interaction increases with the increasing of the concentrations of Tm3+ and Ho3+.