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Nb3Bi crystallizes in the cubic Pm-3n space group. The structure is three-dimensional. Nb is bonded in a 6-coordinate geometry to two equivalent Nb and four equivalent Bi atoms. Both Nb–Nb bond lengths are 2.69 Å. All Nb–Bi bond lengths are 3.01 Å. Bi is bonded to twelve equivalent Nb atoms to form a mixture of edge and face-sharing BiNb12 cuboctahedra.
Nb3Bi crystallizes in the orthorhombic Cmmm space group. The structure is three-dimensional. there are two inequivalent Nb sites. In the first Nb site, Nb is bonded in a 4-coordinate geometry to two equivalent Nb and two equivalent Bi atoms. Both Nb–Nb bond lengths are 2.77 Å. Both Nb–Bi bond lengths are 2.99 Å. In the second Nb site, Nb is bonded in a 8-coordinate geometry to eight Nb atoms. All Nb–Nb bond lengths are 3.11 Å. Bi is bonded in a 4-coordinate geometry to four equivalent Nb atoms.