Efficient anion recognition is of great significance for radioactive 99TcO4- decontamination, but it remains a challenge for traditional sorbents. Herein, we put forward a tactic using soft crystalline cationic material with anion-adaptive dynamics for 99TcO4- sequestration. A cucurbituril-based supramolecular metal-organic material is produced through a multi-component assembly strategy and used as a sorbent for effective trapping of TcO4-. Excellent separation of TcO4-/ReO4- is demonstrated by fast removal kinetics, good sorption capacity and high distribution coefficient. Remarkably, the most superior selectivity among metal-organic materials reported so far, together with good hydrolytic stability, indicates potential for efficient TcO4- removal. The structure incorporating ReO4- reveals that the supramolecular framework undergoes adaptive reconstruction facilitating the effective accommodation of TcO4-/ReO4-. The results highlight opportunities for development of soft anion-adaptive sorbents for highly selective anion decontamination.