Three types of copper sulfides including CuS, Cu7S4 and Cu9S5 were successfully synthesized at different concentrations of ethylenediamine in a liquid phase synthesis process. The whole shape evolution of Cu7S4 microstructures could be manipulated by adjusting the concentration of ethylenediamine. This study indicates that the coordination chemistry of ethylenediamine ligands and copper cations exerts vital effects on the formation of the dendritic structure. Furthermore, experimental conditions such as the reaction temperature and time are also observed to have an impact on the morphology of copper sulfides. The structures of Cu7S4 with snowflake-like morphology provided special paths for ion diffusion. Therefore, apart from the excellent discharge rate and good stability, Cu7S4 also exhibits a high specific capacitance of 1303.01 F g(-1) at a current density of 5 A g(-1).