Two new Cu(I) complexes [CuCl(3-PyOH)(PPh3)(2)] (1) and [Cu-2(mu-Cl)(2)(4-Stpy)(Ph3P)(3)] (2) (PyOH = hydroxypyridine; stpy = styrylpyridine) with triphenylphosphine and pyridine derivatives have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P2(1)/c with a = 9.8945(7), b = 37.266(2), c = 10.9461(7) angstrom, beta = 116.0750(10)degrees, V = 3625.3(4) angstrom(3), Z = 4, D-c = 1.350 Mg/cm(-3), mu = 0.801 mm(-1), F(000) = 1528, the final R = 0.0320 and wR = 0.0729 for 18568 observed reflections (I > 2 sigma(I)), R(all data) = 0.0413, wR(all data) = 0.0769, completeness to theta of 25.01 is 99.9% and GOF = 1.037. Compound 2 crystallizes in monoclinic, space group P2(1)/c with a = 11.290(3), b = 20.388(5), c = 24.092(6) angstrom, beta = 102.028(4)degrees, V = 5424(2) angstrom(3), Z = 4, D-c = 1.428 Mg/cm(-3), mu = 1.016 mm(-1), F(000) = 2408, the final R = 0.0568 and wR = 0.1486 for 27644 observed reflections (I > 2 sigma(I)), R(all data) = 0.0716, wR(all data) = 0.1592, completeness to theta of 25.01 is 99.9% and GOF = 1.056. Two new Cu(I) complexes have been utilized as catalysts for N-arylation of imidazole and both showed good catalytic activity.