To overcome the disadvantages of traditional powder electrodes, such as the insufficient performance, the aggregation of active materials, and the complex fabrication process, rationally constructing free-standing electrode materials with hierarchical architecture is an effective and promising method, which could further improve the electrochemical properties. Herein, using metal-organic framework nanoarrays (MOFNAs) as self-sacrificial templates and SiC nanowires (SiCNWs) network as nanoscale conductive skeletons, we successfully fabricated the hierarchical core-shell SiCNWs@NiCo2O4NAs on carbon cloth (CC) substrate. Taking advantages of structural merits, such as hierarchical porous triangle-like NiCo2O4NAs, the interwoven SiCNWs network and conductive CC substrate, when evaluated as a binder-free supercapacitor electrode, the CC/SiCNWs@NiCo2O4NAs shows a high specific capacitance of 1604.7 F g−1 (specific capacity of 222.9 mA h g−1) at 0.5 A g−1, good rate performance, and excellent cycling stability. Significantly, the hybrid supercapacitor assembled with CC/SiCNWs@NiCo2O4NAs as the cathode and MOF derived CC/SiCNWs@CNAs as the anode, could deliver a high specific density of 49.9 W h kg−1 at a specific power of 800 W kg−1, stable cycling performance, and good flexibility. Impressively, this feasible strategy for fabricating hierarchical structure displays great potential in the field of energy storage.