RhBi4 crystallizes in the cubic Ia-3d space group. The structure is three-dimensional and consists of two RhBi4 frameworks. Rh is bonded in a body-centered cubic geometry to eight equivalent Bi atoms. There are four shorter (2.87 Å) and four longer (2.89 Å) Rh–Bi bond lengths. Bi is bonded in a distorted water-like geometry to two equivalent Rh atoms.