A new bismuth-based fluorous metal-organic framework, [Bi(OOCC6F5)3(C10H8N2)(H2O)2], (OOCC6F5=pentafluorobenzoate,C10H8N2=2,2′-bipyridine)(1) is synthesized by a hydrothermal method. Compound 1 crystalizes in the P21/c space group, exhibiting a two-dimensional supramolecular architecture by intermolecular CH⋯FC interactions between the hydrogen atoms in 2,2′-bipyridine and fluorine atoms in adjacent perfluorophenyl rings. In addition, compound 1 shows excellent properties of degradation Congo red in the absence of UV–vis radiation. Moreover, adsorption kinetics study suggested that the adsorption of Congo red belongs to first-order reaction kinetics. Our results indicated that bismuth-based FMOFs could be promising candidates for the development of efficient degradation of organic dye.