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Poly(pyridinium salts) (PPSs) with positive charges on the backbones were designed and synthesized from the transformation of bispyrylium salts. Such materials exhibited good uptake capacity for rhenium capture from water, and excellent selectivity of ReO 4 − from competing anions. Furthermore, the advantages of facile synthesis and large-scale preparation make this material promising for practical use in industry. 

Rhenium is one of the most valuable elements found in nature, and its capture and recycle are highly desirable for resource recovery. However, the effective and efficient collection of this material from industrial waste remains quite challenging. Herein, a tetraphenylmethane‐based cationic polymeric network (CPN‐tpm) nanotrap is designed, synthesized, and evaluated for ReO₄⁻recovery. 3D building units are used to construct imidazolium salt‐based polymers with positive charges, which yields a record maximum uptake capacity of 1133 mg g⁻¹for ReO₄⁻collection as well as fast kinetics ReO₄⁻uptake. The sorption equilibrium is reached within 20 min and ak_dvalue of 8.5 × 10⁵mL g⁻¹is obtained. The sorption capacity of CPN‐tpm remains stable over a wide range of pH values and the removal efficiency exceeds 60% for pH levels below 2. Moreover, CPN‐tpm exhibits good recyclability for at least five cycles of the sorption–desorption process. This work provides a new route for constructing a kind of new high‐performance polymeric material for rhenium recovery and rhenium‐contained industrial wastewater treatment.