Atomically precise metal clusters are now in the research spotlight, owing to the precise correlation between the physicochemical properties and their atomic-packing structures at an atomic-level. Herein we synthesized an Au-8 cluster capped by four ferrocene ligands (DPPF), in which the ferrocene not only can direct the precise formation of the Au-8 cluster, but also can solidify the structural pattern of the Au, cluster. The Au-8(DPPF)(4) clusters as heterogeneous catalysts can achieve efficiently catalytic performances for the CO oxidation reaction, mainly due to the resistance to aggregation into large particles under reaction conditions. Our results suggest that the homolytic phosphine dissociation nature and the postdissociation reconstruction effect induced by Fe may enhance the catalytic performances of Au-8(DPPF)(4).