Realgar, As4S4, reacts with Cr(CO)(5)THF under cage degradation to give As4S3 center dot Cr(CO)(5) (1). The reverse structural change is found if solutions of 1 in CH2Cl2 react with equimolar amounts of PAs3S3 center dot W(CO)(5) and CuX (X = Cl, Br, I) in CH3CN under biphasic diffusion conditions. The resulting coordination polymers 2-4 contain a reconstituted realgar molecule along with the PAs3S3 cage. The crystal structures of (CuX)(As4S4)(PAs3S3) (X = Cl: 2; Br: 3) are characterized by one-dimensional (1D) (CuX)(As4S4) strands, which are formed by alternating As4S4 cages and CuX dumbbells. Terminal PAs3S3 molecules are coordinated to copper by apical phosphorus and bridging realgar through sulfur. The As-3 triangles of the resulting (CuX)(As4S4)(PAs3S3) strands interact with halides of neighbored strands to give a folded three-dimensional (3D) network. The structure of (CuI)(3)(As4S4)(PAs3S3) (4) contains 1D (Cu3I3) strands as backbones, which are bridged by sulfur atoms of two eta(1:2)-As4S4 molecules while PAs3S3 confines the resulting sheet. The As-3 triangles at the surface of the layers interact with iodide of the next layer to form a layered 3D network.