Two cuprous complexes Cu(L1)(PPh3)1 (1) and Cu(L2)(PPh3)I (2) were obtained by reaction of Cu(PPh3)(3)I (PPh3 = triphenylphosphine) with two different alpha-diimine ligands L-1(3,5-di(2-pyridyl)-4-amino-1,2,4-triazole) and L-2(N-benzylidene-3,5-di (2'-pyridyl)-4-amino-1,2,4-triazole, respectively. These two complexes have been characterized by UV-Vis, luminescence, H-1 NMR spectroscopy and cyclic voltammetric studies. The structures are confirmed by the single crystal X-ray diffraction study. The compound Cu(L1)(PPh3)I (1) crystallizes in the triclinic space group P-1 with a=8.3188(14), b=9.2243(15), c=21.177(4), a=78.156(3), beta=86.45(3), gamma=65.966(3), Z=2 and the compound Cu(L2)(PPh3)I (2) crystallizes in the triclinic space group P-1 with a 8.9671(7), b = 13.9737(11), c = 14.6850(12), alpha = 82.2580(10), beta = 75.7020(10), gamma = 72.2790(10), Z = 2. Both complexes show an MLCT band at 340 similar to 545 nm region and complex 2 exhibits luminescence at room temperature in a dichloromethane solution. The cyclic voltammogram of Cu(L1)(PPh3)I shows the redox couples at + 0.36 and - 0.545 V.