A porous cationic Ag(I) coordination polymer, [Ag(1,2,4,5-p4b)](SbF 6) (TJNU-302) with the ligand 1,2,4,5-p4b (1,2,4,5-tetra(pyridin-4-yl)benzene), is reported, which shows high sorption capacity (211 mg g-1) and distribution coefficient K d (5.8 × 10 5 mL g-1) as well as outstanding selectivity in 500 times excess of CO 3 2or PO 4 3anion for perrhenate removal. TJNU-302 can act as a crystalline turn-off sensor for perrhenate upon UV radiation. In this way, a test paper strip for sensing ReO 4could be produced. In water solution, TJNU-302 shows efficient fluorescence quenching response to ReO 4ion, with the highest quenching percentage (86%) among all reported ReO 4sensors. These results could be elucidated by the bonding properties of single-crystal structures of TJNU-302 before and after perrhenate sorption, as well as density functional theory (DFT) calculations.