Based on the first-principles approach, this Letter reports that the ground state geometry of the Ni@Au₆ cluster forms chair-like conformation, which is distinctly different than the Pd@Au₆ and Pt@Au₆ clusters, where hexagonal planar structure is favored over non-planar isomers. The higher stability of the chairlike conformation has been verified through various complementary basis sets and methodologies. Further investigations were carried out to show the stability of a cluster assembled material (CAM) based on these small clusters and the CO oxidation reaction was carried out to establish their uses as an industrial catalyst.