Bio-composites represent a versatile material with an inescapable solution to the creation of a low-carbon green concept. This research utilised natural Moso bamboo powder as raw material, pre-treated with acetic acid and ball-milling it with different concentrations. Thermal forming was then adopted to synthesise a compact glue-free bio-composite with excellent waterproof and mechanical characteristics. The material obtained better thermal conductivity and stronger mechanical properties after acetic acid ball milling than the untreated bio-composite, and the tensile strength was double that of the untreated bio-composite. It was also found that the water absorption rate of the pre-treated bio-composite was only 8.9% after being immersed in water for one day. Furthermore, the bamboo cell structure of the bio-composite was destroyed and more compact in the subsequent hot pressing, as observed from the micromorphology examination. In addition, the resulting bio-composite has high specific strength and demonstrates green characteristics for environmental protection. Overall, this bamboo-derived bio-composite shows desirable features that have potentially broad application prospects in construction and furniture.