The breakup behaviors of aqueous droplets with surfactant in oil under direct current (DC) electric field are investigated in this paper. Four different droplet breakup modes were observed, namely conical shape-conical jetting, ellipsoidal shape-conical jetting, ellipsoidal shape-filamentous breakup and cylindrical shape-filamentous breakup. The conversion of breakup modes was discussed with the electric capillary number (Ca)-surfactant concentration (CSDBS) phase diagram and the droplet elongation process. The mechanism validated here is that the lobes appear in all breakup modes, and the liquid volume at the both ends of droplet differentiate the breakup modes under different conditions. Different from previous studies, the criterion of droplet breakup modes was proposed based on the interfacial dynamics instead of the bulk phase properties. By analogy with stress–strain relationship, it is found that the electrostatic pressure shows a linear relationship with droplet specific surface area during the droplet elongation process, and the slope K could be employed to identify different breakup modes. These findings are of great significance to the promotion and application of electric-induced droplet breakup.