Ho-doped and Ho,Pr co-doped BaF2 crystals were grown using the temperature gradient technique. The absorption spectra, fluorescence spectra, and fluorescence lifetimes were measured and analyzed. For Ho-doped BaF2, 1.0 at.% Ho:BaF2 showed the best luminescence performance in the 3 μm band. After co-doping with Pr3+, the lower-level lifetime of Ho3+ ions in the 3 μm band was significantly reduced, while the upper laser level lifetime was minimally affected, indicating that Pr3+ ions can be effectively used as a deactivating ion of Ho3+ ions in the BaF2 matrix. For 1.5 at.% Ho, 0.1 at.% Pr:BaF2, the lifetime ratio of the upper and lower levels was 0.47, effectively realizing population inversion.