Rational design of self-supported electrode materials is important to develop high-performance supercapacitors. Herein, a free-standing MnCo2S4@CoNi LDH (MCS@CN LDH) core-shell heterostructure is successfully prepared on Ni foam using the hydrothermal reaction and electrodeposition. In this architecture, the inner MnCo2S4 nanotube provides an ultra-high electrical conductivity and the CoNi LDH nanosheets can offer more electrochemical active sites for better faradaic reactions. Moreover, the core-shell heterostructure can also maintain the structural integrity during the processes of continuous charge/discharge. The MCS@CN LDH electrode displays a satisfactory specific capacitance of 1206 C g-1 and excellent cycling performance with ∼92% retention after 10 000 cycles. In addition, an asymmetric supercapacitor (ASC), in which MCS@CN LDH and N-doped rGO are used as the positive electrode and the negative electrode, was assembled which exhibits an energy density of 48.8 W h kg-1 with superior cycling stability, indicating the potential of this electrode in practical energy storage.