The title compound, [Cu2(μ2-O2CC12H8NO2S)4(CH3CN)2], consists of a dinuclear and centrosymmetric complex based on two CuII atoms coordinated by four 5-nitro-2-phenyl-sulfanyl-benzoate anions and two aceto-nitrile ligands. Each benzoate anion acts as a bis-monodentate ligand while each aceto-nitrile acts as a monodentate ligand, leading to a square-pyramidal NO4 coordination environment for each CuII atom with the aceto-nitrile N atom at the apex. The intra-molecular Cu⋯Cu distance in the dimer is 2.6478 (3) Å. The cohesion of the crystal structure is ensured by (phen-yl)C-H⋯O(nitro) hydrogen bonds and (phen-yl)C-H⋯π inter-actions.