A 3d-4f luminescent metalorganic framework (MOF), [Tb-2(Cu8I8)(C12H8NO2)(6)(H2O)(4)]center dot 5C(4)H(8)O(2) (4), and three analogues {[La-2(Cu8I8)(C12H8NO2)(6)(C4H8O2)(2)(H2O)(2)]center dot 3C(4)H(8)O(2 center dot)2H(2)O (1), [Ce-2(Cu8I8)(C12H8NO2)(6)(H2O)(4)]center dot 5C(4)H(8)O(2) (2), and [Eu-2(Cu8I8)(C12H8NO2)(6)(H2O)(4)]center dot 5C(4)H(8)O(2) (3)}, were self-assembled from copper(I) halide clusters and lanthanide metal ions with an organic linker [3-(pyridin-4-yl)benzoic acid] under solvothermal conditions. Compound 4 with high quantum yield (Phi = 68%) exhibits reversible luminescence behavior, accompanying the removal and recovery of guest molecules (1,4-dioxane). Because of the unique porous structure and dual luminescent centers of compound 4, it can efficiently differentiate benzene series with different sizes and provide readouts in corresponding optical signals. Furthermore, it also can unambiguously discriminate the isomers, homologues, and other small molecules with similar structural motifs from one another. The luminescent color of the MOF sensor in different guest solvents has obvious changes that can be clearly distinguished by the naked eye. This multicolor luminescence originates from emissions of the dual luminescent centers, and the emissions have shifted, enhanced, weakened, or quenched to different degrees.