First examples of the coordination chemistry of the PAs3S3 cage were obtained from solutions of PAs3S3 center dot W(CO)(5) (1) in CH2Cl2 or CH2Cl2/toluene and CuX (X = Cl, Br, I) in MeCN through interdiffiision techniques. Crystals of [Cu(PAs3S3)(4)]X (2, X = Cl; 3, X = Br) and [(Cu2I)(PAs3S3)(3)]I (4) were obtained and characterized by Raman spectroscopy (2) and single-crystal X-ray crystallography. The solid-state structures reveal an unexpected coordination versatility of the PAs3S3 ligand: apical phosphorus and bridging sulfur atoms interact with copper, while As center dot center dot center dot X interactions determine the dimensionality of the frameworks. The structures of 2 and 3 contain tetrahedral [(PAs3S3)(4)Cu](+) cations as secondary building units (SBUs), which are arranged by interactions with Cl- or Br- anions into two- and three-dimensional substructures. These interpenetrate into a (2D + 3D) polycatenane. Compound 4 is built up by a one-dimensional [(Cu2I)(PAs3S3)(3)](n)(n+) ribbon with PAs3S3 cages as P,S-linkers. The As atoms of the exo PAs3S4 linkers interact with iodide counterions (3.35 < d(As-I) < 3.59 angstrom). The resulting two-dimensional layer is organized by weak As center dot center dot center dot I interactions (d(As-I = 3.87 angstrom) into a 3D network.