Tetranuclear [Cu4I4 {(S,S)-Pr-i-pybox}(2)] (1) and dinuclear [Cu2Cl-{(S,S)-Pr-i- pybox}(2)][CuCl2] (2) copper(I) complexes have been synthesized by reaction of Pr-i-pybox with CuI and CuCl, respectively. Furthermore, dinuclear [Cu-2( R-pybox)(2)][PF6](2) [R-pybox = (R,R)-Ph-pybox (3), (S,S)-Pr-i-pybox (4)] and mononuclear complexes [Cu(R-pybox)(2)][PF6][R-pybox = (R,R)-Ph-pybox (5), (S,S) Pr-i-pybox (6)] have been prepared by reaction of [Cu(MeCN)(4)][ PF6] and the corresponding pybox. The structures of complexes 1-3 have been determined by X-ray diffraction analyses.