Calcium fluoride (CaF2) crystalline powders were successfully prepared by the combustion synthesis method. The powder material containing luminescent rare-earth ions, more specifically terbium (Tb3+) and ytterbium (Yb3+), was studied by X-ray diffraction, scanning electronic microscopy and optical spectroscopy. These ions are allocated in charge compensated interstitial positions of tetragonal (C-4v) and trigonal (C-3v) symmetry sites of the cubic (Oh) CaF2 lattice. Up-conversion (UC) luminescence in Tb3+ was achieved using a low power diode laser operating at 975 nm. Tb3+ is insensitive to near-infrared radiation but UC can be achieved via energy transfer from pairs of Yb3+. ions to TO ions. The UC luminescence dynamics of Tb3+ was used to study the energy transfer mechanism. (C) 2015 Elsevier Ltd. All rights reserved.