The ternary antimonide CeNiSb3 has been prepared from an Sb flux or from reaction of Ce, NiSb, and Sb above 1123K. It crystallizes in the orthorhombic space group Pbcm with Z=12 and lattice parameters a=12.6340(7)Å, b=6.2037(3)Å, and c=18.3698(9)Å at 193K. Its structure consists of buckled square nets of Sb atoms and layers of highly distorted edge- and face-sharing NiSb6 octahedra. Located between the ∞2[Sb] and ∞2[NiSb2] layers are the Ce atoms, in monocapped square antiprismatic coordination. There is an extensive network of Sb-Sb bonding with distances varying between 3.0 and 3.4Å. The structure is related to that of RECrSb3 but with a different stacking of the metal-centered octahedra. Resistivity measurements reveal a shallow minimum near 25K that is suggestive of Kondo lattice behavior, followed by a sharp decrease below 6K. © 2003 Elsevier Inc. All rights reserved.