Synthesis of stable hybrid carbon nanostructure for high-performance supercapacitor electrode with long life-cycle for electronic and energy storage devices is a real challenge. Here, we present a one-step synthesis method to produce conductive boron-doped hybrid carbon nanowalls (HCNWs), where sp2-bonded graphene has been integrated with and over a three-dimensional curved wall-like network of sp3-bonded diamond. The spectroscopic studies such as X-ray absorption, Raman, and X-ray photoelectrons clearly reveal the coexistence of diamond and graphene in these nanowalls, while the detailed transmission electron microscopy studies confirm the unique microstructure where a diamond nanowall is encased by a multilayered graphene. Interestingly, these HCNWs yield a high double layer capacitance value of 0.43 mF cm-2 and electrode retention of 98\% over 10 000 cycles of charging/discharging in 1 M Na2SO4 electrolyte. The remarkable supercapacitive performance can be attributed to the 3D interconnected network of diamond nanowalls surrounded by highly conducting graphene. © 2019 American Chemical Society.