The tetragonal layered transition metal copper−molybdenum sulfide Cu 2 MoS 4 (CMS) possesses a high theoretical electrochemical potential because of its abundant redox properties and large layered surface area, which is favorable for ion adsorption/desorption and transport. Cu 2 MoS 4 contains P and I phases, exhibiting different crystal structures, ion transport characteristics, and electrochemical properties accordingly. In this work, for the first time, Cu 2 MoS 4 electrode materials with dual-phase compositions are designed and prepared for supercapacitor application, providing a synergistic effect with high electron transport efficiency and structural stability. Upon an in-depth optimization process, the optimal CMS-4 sample having P and I phases coexisting yields the optimal electrochemical behavior. The CMS-4@carbon cloth (CC) electrode provides a specific capacity of 33.9 mAh g −1 at 1 A g −1 , which is 12.6 and 4.0 times higher than the pure P and I phases, respectively. The assembled MnO 2 @CC//CMS-4@CC supercapacitor exhibits a high energy density of 16.8 Wh kg −1 at 800 W kg −1 power density. The results demonstrate that two-phase coexistence of Cu 2 MoS 4 significantly enhances the electrochemical activities owing to the synergistic effects of P and I phases and provides a promising material for supercapacitor negative electrodes.