Benzotriazoles (BTs) attract increasing concerns because of abundant presence in environmental water bodies. In this study, degradation of 1H-benzotriazole (1H-BT) was performed by a customized vacuum ultraviolet (VUV) device emitting 185 + 254 nm (VUV/UV-C) irradiation. Degradation of 1H-BT presented an apparent rate constant reached 8.17 × 10−4 s−1. Degradation mechanisms included 185 + 254 nm photodegradation and radical reaction. The later one may be the predominant one, which presented a k·OH-1H-BT at (7.3 ± 0.8) × 109 M−1 s−1. Effects of anions revealed that VUV interception and radical trapping were the dominant restraining factors. Degradation of 1H-BT can be attributed to VUV induced radical-based oxidation. Radical-induced addition, substitution and fracture generated abundant hydroxylated and open-loop products during 10–45 min. Identification using reactive oxygen species and apoptosis in Escherichia coli was conducted. Variations of these two indicators revealed that the incomplete degradation products presented higher toxicities than 1H-BT, and a further mineralization reduced their toxicities. In the pure water solution with little impurities, VUV can induce efficient degradation of 1H-BT, suggesting its potential for eliminating and detoxifying MPs.