Inspired by the hierarchical architecture of spider silk, this study introduces a biobased macromolecular composite that combines mechanical flexibility, thermal regulation, and electrical performance. The composite is constructed using a delignified bamboo scaffold, which acts as a naturally aligned, mesoporous framework of cellulose-based macromolecules, integrated with carboxylated multiwalled carbon nanotubes and poly (vinyl alcohol). This design yields a mechanically resilient macromolecular network with stable electrical conductivity under cyclic deformation. The composite achieves enhanced thermal conductivity and demonstrates a 7.29% increase in ice-melting efficiency. Importantly, under prolonged thermal exposure, the composite undergoes thermal degradation, forming a protective carbonaceous char layer that suppresses combustion and reduces CO2 and particulate emissions by 37.2 and 84.6%, respectively. The intrinsic mesoporous structure of bamboo provides an ultralight yet robust template, maintaining mechanical integrity even under cyclic stress. Additionally, the conductive nanomaterials improve interfacial properties, making this composite a promising candidate for durable, biobased flexible electronics and thermally stable structural applications. These multifunctional characteristics highlight the potential of natural macromolecular architectures in developing sustainable, biodegradable, and high-performance polymeric systems for flexible electronics and thermally stable applications.