The identification of thermomechanical in-plane shear behavior of preform is one of the most important factors to ensure the quality of the thermoplastic composites during the thermoforming process. In this present work, the non-symmetric in-plane shear behavior of flax/polypropylene 2D biaxial braided preform for thermoplastic biocomposites was characterized at elevated temperature chamber by using bias-extension test. Analytical models of a bias-extension test based on non-symmetric unit cell geometry for 2D biaxial braids were defined and applied; the thermo-condition-dependent experiments were conducted to study the temperature and displacement rate dependences. The influence of unit cell geometry parameters including braiding angle, tow waviness, and cover factor on the thermal in-plane shear behavior was deeply invested, experiments in both axial and transversal directions were performed for a complete study, and asymmetric scissor mechanisms for in-plane shear behavior were introduced and studied. Finally, a simulation of thermal impregnation distribution based on unit cell geometry was made to clarify the importance of the overall fiber volume fraction.