MgCo2O4 nanoneedles were introduced on the surface of micro and mesoporous silicon carbide flakes (SiCF) to synthesize a supercapacitor with high capacitive performance, made of hybrid electrode materials. Based on the synergistic effect between electric double layer capacitive contributions of SiCF and faradic reaction of MgCo2O4, the SiCF/MgCo2O4 electrode shows outstanding energy storage performance, exhibiting a 310.02 C g−1 of specific stored charge capacity at 5 mV s−1 with high capacity retention ratio over wide range of scan rates (83.2% at 500 mV s−1). Furthermore, in conjunction with a capacitive SiCF negative electrode in a quasi-solid-state PVA-KOHKI gel electrolyte, it resulted in a unique redox-active flexible solid-state asymmetric supercapacitor device. It delivers outstanding capacitive performance (specific stored charge capacity of 185.88 C g−1 at 5 mV s−1), with maximum energy density of 41.308 Wh kg−1 at 464.72 W kg−1 of power density, surpassing many recently reported flexible supercapacitors. Moreover, the ability to operate 3-V green light-emitting diodes (LED) at bending state also indicates its possibility for practical application. Therefore, these novel electrode materials with unique redox-active solid state electrolyte may find promising applications in flexible energy storage devices in future.