Structure parameters of the colquiriite-type fluorides LiCaAlF6 LiSrAlF6 and LiSrGaF6 were studied by means of single crystal X-ray diffraction. Absorption and fluorescence spectra of the Ce-doped fluorides were also measured for correlation with structure differences. The 5d-4f emission spectrum slightly shifts toward the long wavelength side as the distortion around a dopant site becomes appreciable.