Viologen-based metal organic frameworks have generally been used in a variety of applications because of the fact that their counter anions can be exchanged by different anion guests. A cationic [Cd2Cl(m-bpybdc)(2)(H2O)(4)]-(NO3)(3)center dot 7H(2)O (Cd-MOF) (m-bpybdc = 1,1'-bis(3-carboxypheny1)-4,4'-bipyr-idinium) is selected for ion exchanging a series of anions with NO3- in its pore and the resulting hybrids show good structural stability. It is found that the luminescence emission intensity of S2O82-@Cd-MOF [Cd-MOF exchanged with persulfate (S2O82-)] is much stronger than that of parent Cd-MOF and other hybrids Cd-MOF was exchanged by other anions. The results suggest that viologen-based Cd-MOF can be regarded as a luminescent sensor for S(2)O(8)(2- )based on their photoinduced electron transfer process from each other. Cd-MOF shows good selectivity of S2O82- over other anions and sensitivity as well as quick response after 2 min. For the first time, the detection of S2O82- is realized through the luminescence enhancement of viologen-based Cd-MOF. In addition, Cd-MOF displays a certain adsorption ability on Acid Black 1 (419 mg.g(-1)) and methyl blue (484 mg.g(-1)) via the electrostatic interaction between its cationic framework and the aniline anion dyes.