Bismuth fluoride can be prepared by reacting bismuth(III) oxide with hydrofluoric acid:[2] α-BiF3 has a cubic crystalline structure (Pearson symbol cF16, space group Fm-3m, No.

BiF3 is the prototype for the D03 structure, which is adopted by several intermetallics, including Mg3Pr, Cu3Sb, Fe3Si, and AlFe3,[3] as well as by the hydride LaH3.0.

[4] The unit cell is face-centered cubic with Bi at the face centers and vertices, and F at the octahedral site (mid-edges, center), and tetrahedral sites (centers of the 8 sub cubes) - thus the primitive cell contains 4 Bi and 12 F.[5] Alternatively, with the unit cell shifted (1/4,1/4,1/4) the description can be of a fcc cell with face, edge, corner, and centers filled with F, and half (4 of) the octant centers with F, the other half with Bi (each octant type tetrahedrally arranged).

[4] β-BiF3 has the YF3 structure where the bismuth atom has distorted 9 coordination, tricapped trigonal prism.

The addition compound H3BiF6 is hydrolysed by water forming BiOF.