Rationally designed new materials for the selective detection and adsorption of 99Tc, a problematic element in nuclear waste, are important and challenging in environmental monitoring. Here, we utilize an interpenetration approach to develop a cationic fluorescent metal-organic framework (NCU-2), which was constructed by a flexible tridentate nitrogen-containing ligand and Ag+ metal ions. The NCU-2 is a scarce case of 14-fold interpenetrated with excellent chemical stability even under 0.5 M HNO3, which is helpful for the detection and removal of ReO4-/TcO4- from nuclear waste. Excitingly, the fluorescence signal of NCU-2 was obviously quenched in the presence of ReO4- (a nonradioactive surrogate of TcO4-) due to the robust interaction between ReO4- and the host for the formation of a non-fluorescent complex. Furthermore, the NCU-2 exhibits a high selectivity sensing of ReO4- in the presence of excess competitive ions. The superior response of NCU-2 toward ReO4- is ascribed to the high-fold structure and the luxuriant unsaturated Ag metal sites on the wall of 1D pore channels, which can enhance the framework positive charge and accelerate the transport of guest molecules to strengthen the interaction between them. Notably, NCU-2 successfully quantified trace levels of ReO4- in simulated Hanford waste with a broad linear range (0.2-200 μM) and a low detection limit of 66.7 nM. Moreover, NCU-2 also shows a high adsorption capacity to ReO4- (541 mg/g) and rapid sorption kinetics, making it extremely attractive for waste monitoring and emergency remediation.