The hierarchical microstructure evolution of an emerging biobased odd-odd polyamide 5,13 (PA5,13) films under the thermo-mechanical field, stepping from hydrogen bond (H-bond) arrangement to the crystalline morphology, has been investigated systematically. It is found that the reorganization of H-bonds under the thermo-mechanical field plays a crucial role in the crystallization of PA5,13. Especially, it is revealed that the crystallization process under the thermo-mechanical field develops along the chain axis direction, while lamellar fragmentation occurs perpendicular to the chain axis. Consequently, a stable and well-organized H-bond arrangement and lengthened lamellae with significant orientation have been constructed. Laudably, an impressive tensile strength of about 500 MPa and modulus of about 4.7 GPa are thus achieved. The present study could provide important guidance for the industrial-scale manufacture of high-performance biobased odd-odd PAs with long polymethylene segment in the dicarboxylic unit combined with a large difference between the polymethylene segments in the dicarboxylic and diamine units.