This paper reports on the spectroscopic properties and energy transfer of Tm3+/Ho3+-codoped 14Ga2O3-25Bi2O3-20GeO2-31PbO-10PbF2 glasses. The Judd-Ofelt intensity parameters Ωt(t=2，4，6), spontaneous-emission probability, branch ratio and radiative lifetime of each level of Tm3+ have been calculated by Judd-Ofelt theory. The effective bandwidth and peak emission cross-section of the 3H4→3F4 transition (1.47μm) of Tm3+ have also been obtained. Codoping of Ho3+ significantly decreased the population of 3F4 level of Tm3+, while the population of 3H4 level of Tm3+ reduced slightly. Our results indicate that GGBPF glass is a promising candidate for 1.47μm optical amplifiers, and Ho3+ is an effective codopant to enhance the 1.47μm luminescence.