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KBiF6 crystallizes in the cubic Ia-3 space group. The structure is three-dimensional. K1+ is bonded in a 6-coordinate geometry to six equivalent F1- atoms. All K–F bond lengths are 2.74 Å. Bi5+ is bonded in an octahedral geometry to six equivalent F1- atoms. All Bi–F bond lengths are 2.05 Å. F1- is bonded in a bent 150 degrees geometry to one K1+ and one Bi5+ atom.
KBiF6 crystallizes in the tetragonal P-4c2 space group. The structure is three-dimensional. K1+ is bonded in a 8-coordinate geometry to eight F1- atoms. There are four shorter (2.63 Å) and four longer (3.11 Å) K–F bond lengths. Bi5+ is bonded in an octahedral geometry to six F1- atoms. There are four shorter (2.05 Å) and two longer (2.06 Å) Bi–F bond lengths. There are two inequivalent F1- sites. In the first F1- site, F1- is bonded in a distorted bent 150 degrees geometry to one K1+ and one Bi5+ atom. In the second F1- site, F1- is bonded in a distorted single-bond geometry to two equivalent K1+ and one Bi5+ atom.