New tetranuclear supramolecular precursors [(R-C C-C C)Ag](4) (R = Pr-i, Bu-t, and chx) are employed to construct a series of heterometallic silver(I)copper(I) alkyl-1,3-diynyl cluster complexes (1-9) that bear a common CuAg3 core (normally trigonal-planar, but can be interaction under 3.12 angstrom, as found in 1 and 2. The distorted to pyramidal) consolidated by cupro-argentophilic photophysical properties of the multinuclear supramolecular precursors and selected complexes have been investigated The present results strongly suggest that the assembly of medium-nuclearity clusters 3 to 9 is initiated by accretion of additional Ag(I) ions by the ubiquitous CuAg3 template through argentophilic (<3.4 angstrom) interaction, with cooperative cuprophilic enhancement (<2.76 angstrom) in the case of compound 9. To our knowledge, the present study provides the first report of conversion of a Group 11 homonuclear cluster into a heteronuclear one of higher nuclearity via inner-core expansion.