Nanoparticles of intermetallic compounds have attracted much interest because they can exhibit novel electronic and catalytic properties due to their specific crystal structure, ordered atomic arrangement, and quantum effect. Here, gold-tin (AuSn) bimetallic nanoparticles with various mixing ratios were prepared by a co-reduction method using various protective agents (e.g., polymer, amine, phosphine, carboxylic acid, and thiol). Powder X-ray diffractometry and transmission electron microscopy revealed that few-nm-sized, phase-pure Au5Sn intermetallic nanoparticles (IMNPs) were successfully synthesized when Au3+ and Sn2+ precursors with a ratio of 6 : 4 were co-reduced in the presence of oleylamine. The Au5Sn IMNPs thus prepared did not exhibit localized surface plasmon resonance, in contrast to pure Au nanoparticles of comparable sizes. This suggests that interband transition dominates the optical response due to an increase in the density of states near the Fermi level by introducing Sn. The Au5Sn IMNPs supported on mesoporous silica (SBA-15) catalyzed the aerobic oxidation reaction of indanol.