Design and synthesis of hierarchical carbon hybrid based pseudocapacitive electrodes is the next step forward for achieving high-performance supercapacitors. Here, the freestanding electrospun carbon nanofibers/carbon nanotubes/polyaniline (CNFs/CNTs/PANI) ternary composites have been fabricated successfully. Importantly, the hierarchical carbon hybrids by dense CNT forests decorated CNFs serving as supports are crucial for the ternary composites to achieve high electrochemical properties. The hierarchical CNFs/CNTs hybrids serving as inner current collectors can afford plentiful transport channels for more rapidly transporting and collecting electrons, greatly reduce the ion diffusion length, and increase the utilization of pseudocapacitive materials. As expected, the ternary composites as electrodes present high specific capacitance (i.e., 315 F/g at 1 A/g) and dramatic rate capability (i.e., 235 F/g at 32 A/g) in three-electrode configuration. Moreover, the as-fabricated flexible solid-state supercapacitor based on the ternary composites also achieves desired electrochemical properties with high capacitance, high-rate capability, high energy/power density (i.e., 5.1 Wh/kg at 10.1 kW/kg), and remarkable cycling stability (i.e., 92% capacitance retention after 10 000 cycles at 2 A/g). These extraordinary electrochemical properties can be attributed to the well-designed structural advantages and synergistic effects.