Tm3+/Ho3+ co-doped tellurite glasses with the composition of TeO2-ZnO-Na2O are prepared by the high temperature melt-quenching method. The intensity parameters Ωt(t=2,4,6), spontaneous radiative transition rates A, fluorescence branching ratios β and radiation lifetimes τrad of Ho3+ are calculated from the measured absorption spectra with the Judd-Ofelt theory. Meanwhile, the fluorescence spectra of glass samples with different doped concentration of Ho3+ ions are measured, and the results show the intense mid-infrared fluorescence emission around 2.0 μm band in the Tm3+/Ho3+ co-doped tellurite glasses pumped by 808 nm diode laser. The analysis indicates that the mid-infrared emission of Ho3+ ions is mainly the result of resonant energy transfer from Tm3+ to Tm3+ ions, and then zero phonon- and one phonon-assisted nonresonant energy transfer from Tm3+ to Ho3+ ions. The energy transfer micro-rates, critical radius and phonon contributions for the above energy transfer process are calculated and analyzed. Meanwhile, the absorption, stimulated emission cross-sections and gain coefficient of Ho3+5I7→5I8 transitions are calculated. The research shows that Tm3+/Ho3+ co-doped TeO2-ZnO-Na2O glass is a promising host material applied for 2.0 μm-band mid-infrared solid laser.