Perovskite structure compounds are significant candidates for designing new optical function materials due to their structural variability. Here, an inorganic tetravalent cerium fluoride, Na
2CeF
6, is derived from the perovskite structure through double‐site cation co‐substitution. Na
2CeF
6 crystalizes in the non‐centrosymmetric space group
. Edge‐sharing connected NaF
9 and CeF...