In the title compound, [Ag6(C12H10N3OS)6]·4C3H7NO, the hexa-nuclear complex mol-ecule lies about an inversion center. The six Ag atoms form a distorted octa-hedron, with Ag⋯Ag distances in the range 2.933 (1)-3.401 (1) Å. Each Ag atom is surrounded by one N atom and two thiol-ate S atoms from two deprotonated 2-hy-droxy-1-naphthaldehyde thio-semi-carb-a-zone ligands. Each ligand coordinates three Ag atoms via a bridging thiol-ate S atom and a monodentate N atom, thus two Ag3S3 hexa-gonal rings are linked together. Two dimethyl-formamide solvent mol-ecules are located in four sets of sites with half-occupancy and form O⋯H-N hydrogen bonds to the complex mol-ecule. Intra-molecular O-H⋯N hydrogen bonds are also present. The discrete hexa-nuclear clusters are further linked through π-π inter-actions into layers parallel to (001), the shortest distance between the centroids of aromatic rings being 3.698 (2) Å.