A silica-based anion exchange resin was synthesized and used to remove Tc-99 from real radioactive liquid waste. The adsorbent had a uniform particle size and exhibited good thermal stability up to 100 degrees C, which is promising for large-scale column experiments. In accordance with the chemical similarity with Tc, Re was used as a surrogate in this study. The N 1s high-resolution XPS spectra of the adsorbent before and after the adsorption of Re indicated that the ion exchange reaction was the controlling mechanism in the process. After gamma-ray irradiation, the changing trend of the K-d was consistent, which showed that the competitive adsorption of NO3- led to a decrease in K-d. The adsorption capacity for the Re decreased slightly from 35.8 to 31.9 mg/g with the increase in the absorbed dose from 0 to 50 kGy. The separation and recovery of Re and the coexisting ions were achieved by chromatographic separation experiments, and the recovery percentage of Re was 86%. In real radioactive liquid waste, N3/SiO2 exhibited good selectivity toward Tc-99 over the coexisting metals, namely, Sr-90, Cs-137, Am-241, and U, and the decontamination efficiency of Tc-99 attained 65%.