Here we report a novel cobalt doping iron carbon micro electrolysis composite Fe-Co-AC (FCA) that exhibits excellent catalytic performance for the remove of N,N-Dimethylformamide (DMF). The catalytic effects of FCA micro electrolysis (ME), only ozone oxidation (O3), and micro electrolysis synergetic ozonation (ME-O3) on the degradation of DMF were carried out. The results proved that the ME-O3 could obtain high •OH radical yield, showing eminent catalytic efficiency. This is attributed that Co doping optimizes the electron transport path in the material, improves the micro electrolysis synergetic catalytic ozonation performance. Additionally, the relative contribution of reactive oxygen species (ROS) and related reactions were qualitatively evaluated, and the reaction mechanism of ROS generation and pollutant removal was explored. According to the conversion of organic nitrogen and the detection of intermediate, the possible degradation paths of DMF were speculated. The column experiments showed that the ME-O3 process has a certain potential in practical application.