The energy transfer processes between Tb 3þ and Yb 3þ ions are studied in Tb-based fluoride single crystals. These are very transparent from the UV to the IR wavelength regions, except for the characteristic absorption lines of the rare-earth ions under study. In contrast with previously reported Tb 3þ -doped glasses and oxide powders, these crystals containing a high Tb 3þ concentration present two major advantages for the study of the energy transfer processes in the Tb 3þ -Yb 3þ ion pair. Firstly, the adverse influence of host defects is minimized with the use of high quality crystals. Secondly, the high Tb 3þ concentration guarantees a much higher absorption cross-section of UV light, and consequently these crystals have real potential for practical applications. Photoluminescence spectra in the visible-IR wavelength region demonstrate the existence of efficient down and up conversion processes by crossed excitation and emission characteristics of Tb 3þ and Yb 3þ ions. In the down conversion process, Tb 3þ (, two IR photons are emitted for each Tb 3þ ion deexcited by second-order energy transfer to two Yb 3þ ions. The total quantum efficiency of the down conversion process in the fluoride system is shown to increase linearly with the Yb 3þ concentration, reaching its maximum at the Yb 3þ solubility limit in the fluoride host. Further, efficient up conversion by two-and three-IR photon absorption is observed.