Three new thorium-based MOFs based on 1,2,4,5-tetrakis(4-carboxyphenyl)benzene (H4TCPB) were obtained under a similar reaction system (metal salt, ligand, solvent, and acid are the same). Th(IV) forms the central unit of the MOFs in mononuclear and binuclear clusters, respectively. All the MOFs show blue ligand-based luminescence under an ultraviolet environment. This is the first time that multiple thorium-based MOFs with luminescence have been found with the same ligand.