Pseudocapacitive materials, such as binary metal sulfides show great promise as electrode candidate for energy storage devices due to their higher specific capacitance than mono-metal sulfides and binary metal oxides, but generally suffer from low energy densities when assembled in supercapacitor devices. To push the energy density limit of pseudocapacitive materials in devices, a new class of electrode materials with favorable architectures is strongly needed. Here, a rational design and coaxial growth of Ni-Co-S and polypyrrole on vertically-aligned carbon nanotubes array (VA-CNTs)/3D carbon fiber paper (CFP) is presented as a novel freestanding electrode for supercapacitors. Our study has revealed that the catalyst preparation is the key step and the presence of the Al2O3 buffer layer is essential to the growth of VA-CNTs. The 3D hierarchical VA-CNTs/CFP allows high areal loading and high utilization efficiency of the active materials. The binder-free asymmetric supercapacitor devices with Ni-Co-S/V