Despite bamboo’s noteworthy durability, the incidental effects of smoke treatment on the mechanical properties of bamboo culms, including its underlying mechanisms, have not been fully investigated. This study investigated the effects of smoke treatment on the flexural strength of Madake bamboo’s (Phyllostachys bambusoides) hierarchical structure. Results in small clear specimens displayed an asymmetrical flexural behaviour regardless of the applied treatment, and the parameters of flexural strain and specific energy absorption, demonstrated by modulus of elasticity and modulus of rupture, were found to differ. Concerning compression, parenchyma cells had good ability to absorb large deformation, indicated by their large increase in specific energy absorption. In addition, a distinct difference was found between smoke-treated bamboo and untreated bamboo as the capacity of its outermost fibres to withstand greater tensile load was impaired, indicated by the reduction in flexural strain. Thermal degradation caused an increase in the hydrophobicity of bamboo’s outermost layers, thereby engendering higher brittleness in the smoked bamboo. This work highlights critical changes in the mechanical properties of smoked bamboo, which can be addressed in future studies to improve its strength as a sustainable construction material.