Abstract The integration of bio‐inspired hierarchical design into synthetic carbon materials holds promise for developing lightweight, high‐performance structural materials. Hierarchical and heterogeneous nanoscale units are crucial to load bearing and mechanical functionality yet receives limited attention for difficulties in accurate regulation. Herein, one kind of multilayered heterogeneous have proposed pyrocarbon based composite constructed through chemical vapor deposition method with nanoscale graphene orderliness regulation. Sequential construction from orientational graphene sheets to nondirective isotropic networks is achieved through controlling the size and morphology of pyrolysis intermediates with moderate oxidation, being expected to facilitate load transfer and structural stability through dynamically adjustment in heterogeneous interfacial sliding. The resulting multilayer heterogeneous phases exhibit impressive strengthening and toughening mechanisms dominated by microstructural multiscale coupling, which provides new solutions for developing structural composites for high‐temperature aerospace applications. Additionally, the multiple internal reflections arising from the abundant heterogeneous interfaces significantly improve the efficiency of electromagnetic microwave absorption. The multilayered heterogeneous interfaces achieved through orderliness manipulation offer novel insights into the assembly of mechanical functionality integration for wide‐temperature applications and high‐performance macroscopic carbon‐based composites.