[en] Highlights: • An acentric ferroelectric MOF has been successfully synthesized. • The structure of 1 is composed of a 2D inorganic Pb–O–Pb layer and two μ₆-TDC^2- anions pillars.. • 1 is the first example of ferroelectric H₂TDC-based MOF. - Abstract: Self-assembly reaction of Pb(NO₃)₂ with thiophene-2, 5-dicarboxylic acid (H₂TDC) led to an acentric three-dimensional (3D) metal-organic framework under solvothermal conditions, namely, Pb(TDC) (1). The 3D framework of 1 is a pillared-layer structure with the I²O¹ type which is composed of a 2D inorganic Pb–O–Pb substructural layer and two independent μ₆-TDC^2- anions pillars. This 3D framework shows a six-connected pcu topological net according to the topological analysis. Compound 1 crystallizes in an acentric space group and displays potential ferroelectric property which could be due to the swing of the thiophene rings. The remnant polarization (P_r), coercive field (E_c) and saturation spontaneous polarization (P_s) of 1 are ca. 0.034 μC cm⁻², 15.7 kV cm⁻¹ and 0.0997 μC cm⁻², respectively. Among the H₂TDC-based MOFs, the present compound is the first example which shows ferroelectric property. In addition, 1 also exhibits photoluminescent property which can be attributed to ligand-to-metal charge transfer.