Six new complexes, [Cu 4I 4(PPh 2Cy) 4]·2H 2O ( 1), [CuI(PPhCy 2) 2] ( 2), [CuCl(PPhCy 2) 2] ( 3), and [CuBr(PPh 3) 3]·CH 3CN ( 4), [Ag(PPhCy 2) 2(NO 3)] ( 5), [Ag(PCy 3)(NO 3)] 2 ( 6) [where Ph = phenyl, Cy = cyclohexyl], have been synthesized and structurally characterized by X-ray diffraction, IR absorption spectra and NMR spectroscopic studies (except complex 4). The X-ray diffraction analysis of complex ( 1), pseudo polymorph of complex [Cu 4I 4(PPh 2Cy) 4], reveals a stella quadrangula structure. The four corners of the cube are occupied by copper(I) atoms and four I atoms are present at the alternative corners of the cube, further more the copper(I) atoms are coordinated to a monodentate tertiary phosphine. Complexes ( 2) and ( 3) are isostructural with trigonal planar geometry around the copper(I) atom. The crystal structure of complex ( 4) is a pseudo polymorph of complex [CuBr(PPh 3) 3] and the geometrical environment around the copper(I) centre is distorted tetrahedral. In the Ag I complexes ( 5) and ( 6), the central metal atoms have pseudo tetrahedral and trigonal planar geometry, respectively. Spectroscopic and microanalysis results are consistent with the single crystal X-ray diffraction studies.