The activation process of the B(OH)(3)-activated H2O2 solution and its performance toward toxic industrial chemicals (TICs) and chemical warfare agents (CWAs) were investigated to find an efficient way to destroy TICs and CWAs. 11B NMR analysis proved that B(OH)3 reacted rapidly with basic H2O2 to produce peroxoborates ([B (OH)(4_)(00H)A 1, and the proportional contents were closely related to the pH and temperature. O-1(2) and 02 were generated, and their production increased exponentially with pH. TICs thioanisole and paraoxon were used as simulants of CWAs to investigate the decontamination performance and nucleophilic/oxidizing reactivity of the B(OH)3-activated H2O2. Batch experiments proved that peroxoborates acted as the oxidants for the primary oxidation of the sulfide at a pH range of 8-12 and that .O-2(-) was responsible for the further oxidation of sulfoxide. Paraoxon degraded through OOH--mediated SN2 displacement with high stereo -selectivity, and the degradation rate increased exponentially with pH. Mustard gas, soman, and VX degraded effectively into nontoxic products in the B(OH)3-activated H2O2 solution. A pH of 9-11 was recommended as the suitable acidity for developing the B(OH)3-activated H2O2 solution to be a candidate for nucleophilic/oxidizing decontaminant, with advantages in rapid activation and low loss rate of reactive oxygen species.