CaF2:Er nanocomposites have been synthesized using simple co-precipitation method. In order to prepare polyvinyl alcohol (PVA)/CaF2:Er nanofibers, CaF2:Er nanocomposites have been added to the matrix of PVA polymer. PVA/CaF2:Er composite nanofibers have been successfully prepared by electrospinning technique. X-ray diffraction pattern and transmission electron microscopy images indicate that CaF2:Er nanocomposite has been formed with cubic phase and the average crystalline size has been calculated to be about 26-28 nm using the Scherrer's equation. The nanofibers have been characterized using scanning electron microscopy, atomic force microscopy, photoluminescence and UV-visible spectroscopy. Images show that the diameter of fine nanofibers is in the range of 60-110 nm. The photoluminescence spectrum of PVA/CaF2:Er nanofibers exhibits excellent luminescence properties and also shows (4)G11/2 -(4)I15/2 (390 nm) transition as the most prominent group.