A new quaternary dicerium lithium/nickel disilicide, Ce2Li0.39Ni1.61Si2, crystallizes as a new structure type of intermetallic compounds closely related to the AlB2family. The crystal–chemical interrelationships between parent AlB2-type, BaLiSi, ZrBeSi and the title compound are discussed using the Bärnighausen formalism. Two Ce atoms occupy sites of 3m. symmetry. The remainder,i.e.Ni, mixed Ni/Li and Si atoms, occupy sites of \overline{6}m2 symmetry. The environment of the Ce atom is an 18-vertex polyhedron and the Ni, Ni/Li and Si atoms are enclosed in tricapped trigonal prisms. The title structure can be assigned to class No. 10 (trigonal prism and its derivatives) according to the Krypyakevich classification scheme [Krypyakevich (1977). InStructure Types of Intermetallic Compounds. Moscow: Nauka]. The electronic structure of the title compound was calculated using the tight-binding linear muffin-tin orbital method in the atomic spheres approximation (TB-LMTO-ASA). Metallic bonding is dominant in this compound. The strongest interactions are Ni—Si and Ce—Si.