In this work, we report a template-directed self-assembly strategy towards the gram-level synthesis of hierarchically ordered carbon tube-sheet superstructure (CTSS) by using MoO3 nanorod as the template and polyimide (PI) as the carbon source. Even in large quantities, MoO3 nanorods can guide the assembly of PI in solution into vertically oriented nanosheet arrays with periodic patterns, which can be converted to nitrogen-doped porous CTSS after the removal of template and thermal carbonization. Possessing hierarchically ordered architecture, rich porosity and high nitrogen content, CTSS is an appealing material for energy storage and conversion devices such as high-performance lithium ion battery anode and water splitting catalyst support. More importantly, the results in this work highlight an avenue for the controllable synthesis of hierarchically ordered carbon superstructures with diversified functions and applications.