Ce4Sb3 crystallizes in the cubic I-43d space group. The structure is three-dimensional. Ce is bonded to six equivalent Sb atoms to form a mixture of distorted corner, edge, and face-sharing CeSb6 octahedra. The corner-sharing octahedra tilt angles range from 18–49°. There are three shorter (3.16 Å) and three longer (3.38 Å) Ce–Sb bond lengths. Sb is bonded to eight equivalent Ce atoms to form a mixture of distorted corner, edge, and face-sharing SbCe8 hexagonal bipyramids.