In this study, the imidazole-based poly(ionic liquid)s (PILs) synthesized by one step method has been applied for the enrichment and recovery of Re(VII), a nonradioactive surrogate of Tc(VII). The anions (Cl−) in the materials could be efficiently exchanged by ReO4− and TcO4− in a rather short time. The PILs-Cl-1 and PILs-Cl-2 before and after adsorption were characterized by BET, SEM, FT-IR and XPS. The adsorption performance of Re(VII) was investigated by batch and column experiments. By contrast, PILs-Cl-2 exhibited a better adsorption performance, and the adsorption capacity reached 94.92 mg/g for ReO4−. In the recovery experiment of TcO4−, the maximum recovery rate of PILs-Cl-2 for TcO4− was 99.9%. The excellent regenerative and recyclable performance of PILs-Cl-2 was also evaluated in the column experiment, which provided an important basis for practical application in industrial field. [ABSTRACT FROM AUTHOR]