Abstract In the present paper, the results of the theoretical investigation of the small lithium‐chloride clusters are reported. The geometrical structures, electronic and thermodynamic stability of superalkalis, superhalogens, and their single and double charged ions are obtained using efficient and accurate quantum chemistry methods. Further, low‐lying isomers of the Li n Cl n ( ) clusters and their stability parameters are calculated. Two ways of formation of the Li n Cl n clusters, polymerization of LiCl fragments and combination of superalkalis and superhalogen clusters, are compared. By examination the lattice energy and the average Li‐Cl bond length in rectangular Li n Cl n ( ) clusters, it was concluded that already 50 LiCl are enough to mostly resembles the structure and stability of the bulk LiCl.