Luminescent rare-earth oxyfluoride nanofibers were first prepared used electrospinning technique in this paper. The formation of rare-earth oxyfluoride nanofibers was carried out by calcining rare-earth trifluoroacetic acid/Poly(vinyl pyrrolidone) [R (CF3CO2)3/PVP (R = Eu, Ho)] nanofibers, which were electrospun from the mixture solution of R (CF3CO2)3 and PVP. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD) analyses demonstrated the morphology of the Rare-Earth Oxyfluoride (ROF) nanofibers, thestructure and the cubic crystal in ROF fibers. The characteristic photoluminescence from ROF nanofibers were observed with laser excitation at 290 nm.