Eu(2+)-Yb(3+) co-doped transparent glass-ceramic containing nano-Ca5(PO4)3F (FAP) was prepared in reducing atmosphere. XRD and TEM analysis indicated that nano-FAP about 40 nm precipitated homogeneously in glass matrix after heat treatment. Confirmed by spectroscopy measurements, the crystal-like absorption and emission of Eu(2+) indicated the partition of Eu(2+) into FAP nanocrystals in glass ceramic. NIR emission due to the transition (2)F5/2→(2)F7/2 of Yb(3+) ions (about 980-1100 nm) was observed from glasses under ultraviolet excitation, ascribed to downconversion from Eu(2+) to Yb(3+), which can be enhanced by precipitating nano-FAP crystals. The results indicated that Eu(2+)-Yb(3+) co-doped glass-ceramic embedding with nano-FAP is a promising candidate as downconversion materials for enhancing conversion efficiency of solar cells.