In this study, a novel assisted liquid−phase plasma electrolysis was developed to realize one−step synthesis of popcorn biomass−derived porous carbon/cobalt tetroxide (popcorn−carbon/Co3O4) composites, effectively improving the structural stability and conductivity of Co3O4. The phase structure, morphologies, chemical composition, and weight ratio of the as−prepared popcorn−carbon/Co3O4 composites were systematically analyzed. The results of X−ray diffraction (XRD), Raman spectrometer, Fourier infrared spectrometer (FTIR), X−ray photoelectron spectrometer (XPS), and thermogravimetry analyzer (TG) proved the synthesis of the popcorn−carbon/Co3O4 composites. Co3O4 nanoparticles were distributed relatively uniformly on the popcorn−carbon surface. The electrochemical properties of the popcorn−carbon/Co3O4 composite electrode materials were analyzed for exploring the influence of different Co/C ratios on the electrochemical properties of composites. The results showed that the popcorn−carbon/Co3O4 composite electrode materials prepared under 200:1 mass ratio of Co(NO3)2·6H2O and popcorn−carbon possessed a specific capacitance and specific capacity of almost 1264 F/g (594 C/g) at a current density of 1 A/g, exhibiting a better electrochemical property. The efficient, fast, and novel assisted liquid−phase plasma electrolysis provides a new method for the preparation of composite electrode materials on the supercapacitors.