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The title complex, {[Mn(C14H6O8S2)(C12H8N2)2]·4H2O}n, exhibits a chain-like polymeric structure with 9,10-dioxoanthracene-1,5-disulfonate anions bridging MnII atoms in a bis-monodentate mode. The unique MnII atom is located on a crystallographic centre of inversion. Four N atoms from two chelating 1,10-phenanthroline ligands and two sulfonate O atoms from two symmetry-related 9,10-dioxoanthracene-1,5-disulfonate anions give rise to a slightly distorted octahedral coordination environment around the MnII centre. The centroid of the central ring of the anthraquinone ligand represents another crystallographic centre of inversion. In the crystal structure, interligand π–π stacking [centroid-to-centroid distances 3.532 (1) and 3.497 (3) Å] and intermolecular O—H...O hydrogen-bonding interactions assemble the chains into a three-dimensional supramolecular network.