The flexible electrodes have important potential applications in energy storage of portable electronic devices for their powerful structural properties. In this work, unique flexible films with polypyrrole/carbon nanotube (PPy/CNT) composite homogeneously distributed between graphene (GN) sheets are successfully prepared by flow-assembly of the mixture dispersion of GN and PPy/CNT. In such layered structure, the coaxial PPy/CNT nanocables can not only enlarge the space between GN sheets but also provide pseudo-capacitance to enhance the total capacitance of electrodes. According to the galvanostatic charge/discharge analysis, the mass and volume specific capacitances of GN-PPy/CNT (52wt% PPy/CNT) are 211Fg−1 and 122Fcm−3 at a current density of 0.2Ag−1, higher than those of the GN film (73Fg−1 and 79Fcm−3) and PPy/CNT (164Fg−1 and 67Fcm−3). Significantly, the GN-PPy/CNT electrode shows excellent cycling stability (5% capacity loss after 5000 cycles) due to the flexible GN layer and the rigid CNT core synergistical releasing the intrinsic differential strain of PPy chains during long-term charge/discharge cycles.