With the proposal of a low carbon strategy, spontaneous generation of reactive oxygen species (ROS) via O 2 activation under mild ambient conditions is considered an environmentally friendly and cost-effective technology for an advanced oxidation process. Herein, a novel O 2 activation system based on a defect-rich and boron-doped MoS 2 catalyst (B-MoS 2−x ) was constructed for organics degradation without the addition of oxidants and energy consumption. This system enabled electron transfer from organic pollutants to O 2 under the effect of an interfacial microelectric field, exhibiting high catalytic activity and stability. Even after five-cycle use, the decrease in organics degradation efficiency in the B-MoS 2−x /air system is less than 5%. The long-term RhB elimination experiment is conducted in a homemade continuous-flow membrane-based reactor, which demonstrated that the B-MoS 2−x /air system can be operated continuously and steadily for 48 h. Due to the difference of adsorption energy, O 2 and organics were, respectively, adsorbed on S defect and B, further facilitating activation of O 2 to ROS for organics degradation. Additionally, the turnover frequency of O 2 •− production over B-MoS 2−x reaches 2.93 h −1 , and the biotoxicity of the pollutants is decreased obviously in the B-MoS 2−x /air system. This work provided a new idea to promote the research of the microelectric field for O 2 activation to ROS.