Carbon nanosheets are widely used in electrocatalysis. Structure control is a great challenge in preparation of carbon materials. Here, a facial solid state assembly method is applied to prepare carbon nanosheets. By choosing amino acids as precursors, structure regulation of carbon nanosheets could be realized via switching the side chains of organic linkers, showing structure evolution from dense monolithic to porous nanosheets. Graphene-like carbon nanosheet constructed foam superstructure was also obtained. Owing to high porosity (BET surface area 1680 m2 g−1 with hierarchical pore structure) and nitrogen (8.23 wt%) modified graphitic frameworks, glutamic acid derived nitrogen doped porous carbon nanosheet superstructure showed high ORR activity (onset potential 0.9 V vs. RHE).