The reaction of a triazole ligand, 2-(1H-1,2,3-triazol-4-yl)pyridine (L1), with 2-bromopyridine afforded three new ligands, 2,2'-(1H-1,2,3-triazole-1,4-diyl)dipyridine (L2), 2,2'-(2H-1,2,3-triazole-2,4-diyl)dipyridine (L3) and 2,2'-(1H-1,2,3-triazole-1,5-diyl)dipyridine (L4). A series of luminescent mononuclear copper(I) complexes of these ligands [Cu(Ln)(P^P)](ClO4) [n = 1, P^P = (PPh3)2 (1); n = 1, P^P = POP (2); n = 2, P^P = (PPh3)2 (3); n = 2, P^P = POP (4); n = 3, P^P = (PPh3)2 (5); n = 3, P^P = POP (6); n = 4, P^P = (PPh3)2 (9); n = 4, P^P = POP (10)] have been obtained from the reaction of Ln with [Cu(MeCN)4]ClO4 in the presence of PPh3 and POP. L3 was also found to form dinuclear compounds [Cu2(L3)(PPh3)4](ClO4)2 (7) and [Cu2(L3)(POP)2](ClO4)2 (8). All of the Cu(I) compounds have been characterized by IR, UV/vis, CV, 1H NMR, and 31P{1H} NMR. The molecular structures of 1-3, 5, and 7 have been further determined by X-ray crystallography. In CH2Cl2 solutions, these Cu(I) complexes exhibit tunable green to orange emissions (563-621 nm) upon excitation at λex = 380 nm. In the solid state, these complexes show intense emissions and it is interesting to note that 1 and 3 are blue-light emitters. Density functional theory (DFT) calculations revealed that the lowest energy electronic transition associated with these complexes predominantly originates from metal-to-ligand charge transfer transitions (MLCT).