A series of CaFCl:Tb3+ and CaFCl:Tb3+,A+(A=Li, Na and K) nanophosphors were synthesized by the one-step sol-gel method, which were reported for the first time. The sample consisted of monodisperse particles, the average size of which was 37 nm. The emissions of Tb3+ ions and oxygen defects O F? were demonstrated in the CaFCl:Tb3+ samples. The former was made up of several peaks at 488, 545, 587 and 623 nm, ascribed to 5D4→7F J(J=6–3) transitions of Tb3+ ions. The latter was shown as a broad band peaked at about 450 nm. Alkali metal ions A+(A=Li, Na and K) were introduced as the charge compensators to improve the luminescence of samples. The influence of charge compensators on the emissions of Tb3+ ions and oxygen defects O F? was investigated by the measurement of fluorescence spectra and luminescence decay curves. The results indicated that all the charge compensators weakened the defects emission. Furthermore, Li+ ion was the best charge compensator, because it not only reduced the defects emission but also increased the emission intensity of Tb3+ significantly. Our results suggested that this nanophosphor sensitized by the charge compensator might broaden potential applications of rare-earth doped Ca FCl. A series of CaFCl: Tb3 + and CaFCl: Tb3 +, A + (A = Li, Na and K) nanophosphors were synthesized by the one-step sol- gel method, which were reported for the first time. The sample consisted of monodisperse particles, the average size of which was 37 nm. The emissions of Tb3 + ions and oxygen defects OF? were demonstrated in the CaFCl: Tb3 + samples. The former was made up of several peaks at 488, 545, 587 and 623 nm, ascribed to 5D4 → 7F Alkali metal ions A + (A = Li, Na and K) were introduced as the charge compensators to improve the luminescence (J = 6-3) transitions of Tb3 + ions. The latter was shown as a broad band peaked at about 450 nm of samples. The influence of charge compensators on the emissions of Tb3 + ions and oxygen defects OF? was investigated by the measurement of fluorescence spectra and luminescence decay curves. The results indicated that all the charge compensators weakened the defects emission. the best charge compensator, because it not only reduced t Our results suggested that this nanophosphor sensitized by the charge compensator might broaden potential applications of rare-earth doped Ca FCl.