This study probes into the root cause of split in thermally modified bamboo culm by investigating the underlying effect of thermal contraction with respect to its orthotropic nature by experimental and numerical methods while concurrently monitoring the chemical variation of its structure by Fourier transformed infrared spectroscopy (FTIR). In first part of this study, a non-linear increase in dimensional and weight changes of small clear bamboo specimens were observed with increasing temperature. The dimensional changes in the radial and tangential directions significantly exceeded that in the longitudinal direction. From FTIR results, shrinkage effect between 150 °C to 200 °C was associated with weight loss engendered by reduction in weakly bound water and increase in desorption of water content while alteration of its mechanical properties was attributed to changes in cellulose, hemicellulose, and lignin. From results of finite element method (FEM), the graded variation in thermal expansion coefficient, which showed the formation of a narrowed region of strain concentration corresponding to longitudinal crack propagation, was associated with the inducement of internal forces, namely tensile and compressive forces, at specific regions along the culm length. The results of this study can be useful to achieve optimized durability in modified bamboo for construction.