Based on the first-principles approach, this Letter reports that the ground state geometry of the Ni@Au-6 cluster forms chair-like conformation, which is distinctly different than the Pd@Au-6 and Pt@Au-6 clusters, where hexagonal planar structure is favored over non-planar isomers. The higher stability of the chair-like 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. (C) 2013 Elsevier B. V. All rights reserved.