Nuclear industry spent fuel reprocessing and some radioactive contamination sites often involve high acidity and salinity environments. Currently developed and reported sorbents in 99 TcO4 - sequestration from the nuclear waste are unstable and show low adsorption efficiency in harsh conditions. To address this issue, we developed a post-synthetic modification strategy by grafting imidazole-based ionic liquids (ILs) onto the backbone of covalent organic framework (COF) via vinyl polymerization. The resultant COF-polyILs sorbent exhibits fast adsorption kinetics (<5 min) and good sorption capacity (388 mg g-1 ) for ReO4 - (a nonradioactive surrogate of 99 TcO4 - ). Outstandingly, COF-polyILs composite shows superior ReO4 - removal even under highly acidic conditions and in the presence of excess competing ions of Hanford low-level radioactive waste stream, benefiting from the stable covalent bonds between the COF and polyILs, mass of imidazole rings, and hydrophobic pores in COF.