Two Cu(I) coordination architectures, [(CuI) 4 (L 1 ) 2 ] n (1) and [(CuI) 4 (L 2 ) 1.5 ] n (2) with two structurally related flexible dithioether ligands, 1,4-bis(ethylsulfanyl)butane (L 1 ) and 1,4-bis(benzylsulfanyl)butane (L 2 ) have been synthesized and structurally characterized by element analysis and X-ray diffraction. In both complexes, (CuI) 4 cubane cluster acts as a secondary building unit and dithioether ligands as a ditopic bridge to generate two distinct frameworks. 1 has a two-dimensional (4,4) network, while 2 is a three-dimensional framework with rare 4(6).6(4) topology, being the first example in (CuI) 4 complexes. The difference of frameworks can be attributed to the variation of the terminal groups of the two ligands.