The formation of coordination polymers from copper(I) bromide and P4S3, a potentially tetradentate P‐donor bridging ligand, was studied. Whereas (P4S3)3(CuBr)7 (1) formed in excellent yield, (P4S3)(CuBr)3 (2) and (P4S3)(CuBr) (3) crystallized as mixtures. The new compounds were characterized by X‐ray crystallography and solid‐state 31P MAS NMR spectroscopy. The structure of 1 consists of a 3D network of cylindrical (CuBr)n columns, castellated (CuBr)n chains and diatomic CuBr units. These building blocks are linked by tetradentate P4S3 molecules. The structure of 2 comprises undulated (CuBr)n layers, which are intra‐ and interlayer linked by tridentate P4S3 molecules. Compound 3 is a one‐dimensional polymer composed of four‐membered Cu2Br2 rings, which are bridged by the P3 bases of two P4S3 molecules.