A simple precipitation synthesis of fluoro-elpasolites is reported for the first time. X-ray diffraction results show phase formation for K 2 NaAlF 6 and K 2 LiAlF 6 precipitated from aqueous solutions. Intense Eu 2+ emission in both the hosts is also reported for the first time. K 2 NaAlF 6 exhibits both line and band emissions which are attributed to Eu 2+ at K + and Na + sites, respectively. Only line emission is observed for K 2 LiAlF 6 . The emission is very strong, intensity being comparable to that of a commercial UV lamp phosphor. The photoluminescence spectra are explained on the basis of the known energy level scheme for Eu 2+ . It is suggested that fluoro elpasolite phosphors obtained by the new route can be useful for making further studies on these phosphors.