The reaction of [Cu(NCMe)4][PF6] with aromatic acetylenes HC2R and the triphosphine 1,1,1-tris(diphenylphosphino)methane in the presence of NEt3 results in formation of hexanuclear Cu(I) clusters with general formula [Cu6(C2R)4{(PPh2)3CH}][PF6]2 (R = 4-X-C6H4 (1–5) and C5H4N (6); X = NMe2 (1), OMe (2), H (3), Ph (4), CF3 (5)). The structural motif of the complexes studied consists of a Cu6 metal core, supported by two phosphine ligands and stabilized by σ- and π- coordination of the alkynyl fragments (together with coordination of pyridine nitrogen atoms in cluster 6). The solid state structures of the complexes 2–6 were determined by single crystal XRD analysis. The structures of the complexes in solution were elucidated by 1H, 31P and 1H-1H COSY NMR spectroscopy and ESI mass-spectrometry. The clusters 1–6 exhibit moderately strong phosphorescence in solid state with quantum yield up to 17%. Complexes 1–5 were found to form solvates (acetone, acetonitrile) in the solid state. The coordination of loosely bound solvent molecules strongly affects emission characteristics and leads to solvato- and vapochromic behavior of the clusters. Thus, solvent-free and acetonitrile solvated forms of 3 demonstrate contrasting emission in blue (475 nm) and orange (615 nm) regions, respectively. The computational studies show that alkynyl-centered IL transitions with MLCT ones between Cu6 metal core, alkynyl fragments and triphosphine moiety of these assemblies play a dominant role in formation of excited states.