99Tc primarily exists high mobility in the natural aqueous environment due to its extremely high solubility and non-complexing features, which can easily cause radioactive pollution. We herein report a general strategy for constructing a novel resin (SiPAN-PEI) with multiple positive charges nitrogen, exhibiting ultrafast adsorption kinetics (< 3 min), superior adsorption capacities (463.96 mg g−1), and excellent selectivity in the presence of excess competitive anions, which exceed those of most commercial resins. Moreover, based on impressive structure stability in extreme conditions, SiPAN-PEI can still maintain superior adsorption abilities after suffering irradiation, calcination, and immersion in strong acid. In addition, the separation performance kept excellently after five loading-washing-eluting cycles and the total adsorption ratio can still reach 97 %. Outstandingly, SiPAN-PEI can remove most of ReO4- from simulated nuclear wastewater through a sequential injection automatic separation system and can reduce the concentration of ReO4- to the maximum concentration standard set by the World Health Organization (WHO) in a short time. Leveraging density functional theory calculations and other characteristics clearly elucidated adsorption mechanism of anion-exchange between Cl- and TcO4-/ReO4-. In terms of superior adsorption property, SiPAN-PEI is demonstrated to be a pretty candidate for 99Tc elimination from wastewater.