Crustacean cuticles are receiving extensive attention for its potential in developing environmentally friendly and high energy density electrodes for supercapacitor applications. In the current work, the demineralized tergite cuticle of mantis shrimp was employed as a precursor for the fabrication porous biochar. The structural benefits of the cuticle, including the hierarchical nanofiber networks, and the interpenetrating pore systems were maximumly retained, providing a high carbon content and specific surface area scaffold. Graphene oxide sheets were deposited across the biochar through the pore canal systems to further increase the conductivity of the biochar, forming a novel freestanding carbon composite. Throughout the modification process, the material products were examined by a range of methods, which showed desired structural, chemical and functional properties. Our work demonstrates that high performance carbon materials can be manufactured using a simple and green process to realize the great potential in energy storage applications.