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Core-shell hierarchical structured composites have demonstrated great advantages in numerous energy storage devices. In particular, structured composites with rationally structural components and controllable morphology are the most effective in enhancing electrochemical properties. In this work, MnO 2 @NiCo 2 O 4 @Ti 3 SiC 2 /CC (carbon cloth) core-shell hierarchical structured composites were designed and successfully synthesized via electrospinning followed by a two-step hydrothermal reaction. The Ti 3 SiC 2 /CC nanofibers and core-shell nanoarrays were able to improve the specific capacitance and cycling stability. In the three-electrode system, the specific capacitance of MnO 2 @NiCo 2 O 4 @Ti 3 SiC 2 /CC was observed as 1938.2 F/g at a current density of 1 A/g, while the rate capability retention was observed as 81.7% between 1 and 10 A/g. Furthermore, a superior cycling stability was observed following 5000 cycles with a specific capacitance retention rate of 55.4%. Employing MnO 2 @NiCo 2 O 4 @Ti 3 SiC 2 /CC as the all solid-state supercapacitor positive electrode exhibited a high energy density of 58.0 W h/kg at the power density of 800 W/kg. Results demonstrate the potential of the MnO 2 @NiCo 2 O 4 @Ti 3 SiC 2 /CC as an electrode material with phenomenal electrochemical properties for supercapacitors. [ABSTRACT FROM AUTHOR]