The assembly of superstructures from building blocks is of fundamental importance for engineering materials with distinct morphologies and properties, and deepening our understanding of self-assembly processes in nature. Up to now, it is still a great challenge in materials science to construct multiple-component superstructure with unprecedented architectural complexity and symmetry from molecular. Here, we demonstrate an improved one-pot hydrothermal carbonization of biomass strategy that is capable of fabricating unprecedented asymmetric carbonaceous bivalve-like superstructures with in suit generated solid particles and ordered porous polymers as two kinds of building blocks. In our system, different building blocks can be controllably generated, and they will assemble into complex superstructures through a proposed “cooperative assembly of particles and ordered porous polymers” mechanism. We believe that this assembly principle will open up new potential fields for the synthesis of superstructures with diverse morphologies, compositions, and properties.