Recently, much attention has been drawn in the development of flexible energy storage devices due to the increasing demands for flexible/portable electronic devices with high energy density, low weight, and good flexibility. Herein, vertically oriented graphene nanosheets (VGNs) are in situ fabricated on the surface of free‐standing and flexible Si3N4 nanowires (NWs) membrane by plasma‐enhanced chemical vapor deposition (PECVD), which are directly used as flexible nanoscale conductive substrates. NiCo2O4 hollow nanospheres (HSs) and FeOOH amorphous nanorods (NRs) are finally prepared on Si3N4NWs@VGNs, which are served as the positive and negative electrodes, respectively. Profiting from the structural merits, the synthesized Si3N4NWs@VGNs@NiCo2O4HSs and Si3N4NWs@VGNs@FeOOHNRs membrane electrodes exhibit remarkable electrochemical performance. Using Si3N4NWs membrane as the separator, the assembled all Si3N4NWs membrane‐based flexible solid‐state asymmetric supercapacitor (ASC) with a wide operating potential window of 1.8 V yields the outstanding energy density of 96.3 Wh kg−1, excellent cycling performance (91.7% after 6000 cycles), and good mechanical flexibility. More importantly, this work provides a rational design strategy for the preparation of flexible electrode materials and broadens the applications of Si3N4NWs in the field of energy storage.