Abstract A new flexible aromatic multithiocarboxylate ligand: 1,4-benzenebis(thioacetic acid) (H 2L), was synthesized and introduced to construct three interesting metal–organic frameworks (MOFs) with the photoluminescent properties. Three MOFs were characterized by the elemental analysis, infrared (IR) spectrum, and single crystal X-ray diffraction. [Zn 3L 3(2,2′-bipy) 2] n ( 1) is a two-dimensional (2D) layered architecture that consists of the linear trinuclear units of Zn atoms. [ZnL(2,2′-bipy)(H 2O)] n ·0.7 nH 2O ( 2) is a one-dimensional (1D) helical chain, which further forms a 2D structure with 30-membered ring with a size of 7.64 × 15.53 Å via O−H···O hydrogen bonds. [ZnL(phen)(H 2O)] n ·0.35 nH 2O ( 3) presents a 2D supramolecular network through the O−H···O interactions. Their thermal and photoluminescent properties in solid state were given.