Recent efforts have demonstrated that the construction of hierarchical, uniform carbon-based architecture can largely enhance the electrochemical performance of the electrodes due to their increased surface area and abundant mesopores for mass transport. However, how to achieve well-defined, highly-efficient free-standing carbon electrodes via material design and synthesis exploration remains a challenge. Recently, we have achieved the synthesis of a series of freestanding carbon arrays by using two-dimensional nanosheet nanoarray as templates and catalysts. The as-synthesized binder-free carbon-based electrodes display satisfactory activity and stability in energy storage and conversion. Besides, the carbon arrays can also act as micro-substrate to support electrochemical active materials with ultrahigh mass loading for energy applications.