Bamboo is widely distributed, rapidly regenerable, and incorporates long cellulose fibers, which make it one of the most lightweight and strong natural materials. Processing bamboo into a high-performance structural material for plastic replacement is highly promising but challenging. In this study, an allnatural, high-performance structural material is derived from natural bamboo with superior mechanical and thermal properties that benefit from the introduction of surface charge and further layer-by-layer assembly of bamboo cellulose fibers. The obtained modified bamboo fiber plate (MBFP) transcends the constraints of the natural size and anisotropy of bamboo, showing high flexural strength (ca. 179 MPa) and flexural modulus (ca. 12 GPa). Moreover, the product has an extremely low coefficient of thermal expansion (ca. 11.3 × 10 À 6 K À 1 ), high thermal stability, and superior fire resistance. The excellent mechanical and thermal properties combined with the efficient and rational manufacturing process make MBFP a powerful plastic alternative for furniture, construction, and automotive industries.