We report the synthesis and structures of two 34-atom metal nanoclusters, namely [Ag34(BTCA)3(C[triple bond, length as m-dash]CBu t )9(tfa)4(CH3OH)3]SbF6 and [AuAg33(BTCA)3(C[triple bond, length as m-dash]CBu t )9(tfa)4(CH3OH)3]SbF6, where H4BTCA is p-tert-butylthiacalixarene and tfa is trifluoroacetate. Their compositions and structures have been determined by single-crystal X-ray structural analysis and ESI-MS. The cationic cluster consists of a centered icosahedron M@Ag12 (M = Ag or Au) core that is surrounded by 21 peripheral silver atoms. Surrounding protection is provided by four kinds of ligands, including three BTCA, nine t BuC[triple bond, length as m-dash]C, four tfa, and three methanol solvent ligands. It was found that the Ag5@BTCA μ5-coordination motif of thiacalixarene is critical for high stability of the title clusters, and extra stability enhancement can be achieved by doping a gold atom at the center of the silver cluster. This work suggests that coordination saturation should be taken into account in addition to electronic and geometric factors for analyzing metal nanocluster stabilities.