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The hydrothermal reaction of CoCO3 and 4-fluorobenzoic acid afforded the title CoII complex, [Co(C7H4FO2)2(H2O)2]n. The CoII atom is located on an inversion center and is coordinated by six O atoms from two water molecules and four μ2-carboxylate groups of 4-fluorobenzoate anions, forming a distorted CoO6 octahedron, with Co—O bond lengths in the range 2.071 (2)–2.130 (2) Å. All adjacent O—Co—O angles are in the range 84.78 (6)–95.22 (6)° and opposite angles are 180.0°. Each μ-carboxylate group of the 4-fluorobenzoate anions bridges two symmetry-related CoII atoms. Hydrogen-bonding interactions of the coordinated water molecules further connect the cobalt–carboxylate units, forming layers perpendicular to the a axis. The cobalt–oxygen layers are encased in a sandwich-like fashion by layers of π-stacked 4-fluorobenzoate anions. Within these layers the benzene rings of the 4-fluorobenzoate anions are π-stacked, with centroid–centroid distances of 3.432 (4) Å.