Energy transfer rates and population inversion of I 4 11 / 2 excited state of Er 3 + investigated by means of numerical solutions of the rate equations system in Er : LiYF 4 crystal In this work we present the spectroscopic properties of LiYF 4 ͑YLF͒ single crystals activated with thulium and codoped with ytterbium and neodymium ions. The most important processes that lead to the thulium upconversion emissions in the blue region were identified. A time-resolved luminescence spectroscopy technique was employed to measure the luminescence decays and to determine the most important mechanisms involved in the upconversion process that populates 1 G 4 ͑Tm 3+ ͒ excited state. Analysis of the energy transfer processes dynamics using selective pulsed laser excitations in Yb:Tm:Nd, Tm:Nd, and Tm:Yb YLF crystals shows that the energy transfer from Nd 3+ to Yb 3+ ions is the mechanism responsible for the enhancement in the blue upconversion efficiency in the Yb:Tm:Nd:YLF when compared with the Yb:Tm system. A study of the energy transfer processes in YLF:Yb:Tm:Nd crystal showed that the 1 G 4 excited level is mainly populated by a sequence of two nonradiative energy transfers that start well after the Nd 3+ and Tm 3+ excitations at 797 nm according to NdResults of numerical simulation of the rate equations system showed that a population inversion for 481.4 nm laser emission line is attained for a pumping rate threshold of 26 s −1 , which is equivalent to an intensity of 880 W cm −2 for a continuous laser pumping at 797 nm. On the other hand, a population inversion was not observed for the case of 960 nm ͑Yb 3+ ͒ pumping.