The interactions of Cu(I) and Ag(I) ions with four star-shaped ligands, 2,4,6-tris(N-7-azaindolyl)-1,3,5-triazine (tat), 1,3,5-tris(N-7-azaindolyl)benzene (tab), 2,4,6-tris(2,2′-dipyridylamino)-1,3,5-triazine (tdat) and 1,3,5-tris(2,2′-dipyridylamino)benzene (tdab) have been investigated by X-ray diffraction, NMR and fluorescent spectroscopic analyses. Eight new complexes [Cu(PPh₃)(tat)][BF₄] (1), [Cu(PPh₃)(tab)][BF₄] (2), [Cu(PPh₃)(tdab)][BF₄] (3), {[Cu(PPh₃)₂]₂(tdat)]}[BF₄]₂ (4), (AgNO₃)_1.5(tab) (5), (AgNO₃)₂(tat) (6), (AgNO₃)₄(tdab) (7), and (AgNO₃)₃(tdat)(H₂O)₂ (8) have been isolated from the reactions of [Cu(PPh₃)₂(CH₃CN)₂][BF₄] and AgNO₃ with the corresponding ligands. The structures of compounds 1–7 have been established by single-crystal X-ray diffraction analyses, which show that the central core in the chelate ligand results in distinct structures for both Cu(I) and Ag(I) complexes. All Cu(I) complexes are discrete molecules while all Ag(I) complexes are polymeric with helical, sandwich, or chair-like structures. A variable temperature ¹H NMR study established that the Cu(I) complexes display dynamic exchange in solution. Fluorescent titration experiments showed that the four ligands have distinct responses toward Cu(I) and Ag(I) ions, which may be correlated to the distinct structures of the complexes and the electronic property differences of the ligands.