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In the title compound, {[Cu(C8F4O4)(CH3OH)]·CH3OH}n, two CuII atoms are bridged by four carboxylate groups, forming the well known paddle-wheel secondary building unit (SBU) with axial methanol ligands. In each ligand, the dihedral angles between the benzene ring and the two carboxylate groups are 80.43 (17) and 62.5 (4)°. Within each SBU, the four carboxylate groups come from four symmetry-equivalent tetrafluoroisophthalate ligands. Each tetrafluoroisophthalate group connects two SBUs, forming a layered structure . In the crystal, O—H...O hydrogen bonds involving the free and ligated methanol molecules link the molecules into a three-dimensional supramolecular network.