The bismuth(III) complex of thiosalicylic acid (2-mercaptobenzoic acid; H2L), ammonium tris(2-mercaptobenzoato-O,S) bismuth(III) dihydrate, {(NH4)3[Bi(L)3]粠H2O}, has been prepared and its crystal structure determined. The distorted octahedral tris-bidentate complex unit has pseudo-C3 symmetry with the facially related thiolate sulfur donors providing a regular facial cap to the octahedron (Bi-S 2.595, 2.596, 2.596(5) ũ with the Bi-O(carboxylate) distances less regular (2.715, 2.741, 2.785(15) ũ. The network polymeric structure is stabilized by hydrogen-bonding associations through both the ammonium counter ions and the lattice water molecules.