It is well known that the structure of an electrode material seriously affects its electrochemical performance. In this study, we prepare hybrid structured NiCo₂S₄@PPy nanoarchitectures by a hydrothermal method and subsequent electrodeposition process. The specific capacitance of the obtained sample is 1733.23 C g⁻¹ at 1 A g⁻¹. The assembled asymmetric device presents an energy density of 59.59 W h kg⁻¹ at 1404.04 W kg⁻¹. The excellent electrochemical performance can be attributed to the synergistic effect between the high theoretical specific capacitance of the NiCo₂S₄ sheets and the superior cycling stability of the PPy film. The device also shows an outstanding mechanical flexibility at different bending angles.