A novel Au-12 supramolecule (1(2)) composed of two-, three-, and four-coordinated Au(I) centers was constructed on the S-3 scaffolding (trithiocyanurate, S3C3N3 (3-)). 1(2) can be regarded as a tetramer of the Au-3 unit, [AuP(3-CF3-C6H4)(3)](3)(S3C3N3) by losing four P((3)-CF3-C6H4)(3) ligands upon tetramerization. A congener of the monomer unit [AuP(2-py)(C6H5)(2)](3)(S3C3N3) (2) was also synthesized; X-ray study on 2 revealed in turn a monomer structure.