The widespread occurrence of atrazine (ATZ) in water environments presents a considerable risk to human health and ecosystems. Herein, the performance of dielectric barrier discharge integrated with periodate (DBD/PI) for ATZ decomposition was evaluated. Results demonstrated that the DBD/PI system improved ATZ decomposition efficiency by 18.2–22.5% compared to the sole DBD system. After 10 min treatment, the decomposition efficiency attained 82.4% at a discharge power of 68 W, a PI dosage of 0.02 mM, and an initial ATZ concentration of 10 mg/L. As the PI dosage increased, the decomposition efficiency exhibited a trend of initially increasing, followed by a decrease. Acidic conditions were more favorable for ATZ removal compared to alkaline and neutral conditions. Electron paramagnetic resonance (EPR) was adopted for characterizing the active species produced in the DBD/PI system, and quenching experiments revealed their influence on ATZ decomposition following a sequence of 1O2 > O2−• > IO3• > OH•. The decomposition pathways were proposed based on the theoretical calculations and intermediate identification. Additionally, the toxic effects of ATZ and its intermediates were assessed. This study demonstrates that the DBD/PI treatment represents an effective strategy for the decomposition of ATZ in aquatic environments.