PST (polysynthetic twinned) TiAl crystal exhibits excellent mechanical properties, and thus, it has been regarded as a critical candidate for turbine blades in the aero-engine industry. For the first time, the deformation behavior of PST-TiAl bicrystals with two different α2/γ lamellar orientations was studied in this work. Ti-46Al-6Nb bicrystals were cut from directionally solidified ingots, and three bicrystals of B1 (10°–14°), B2 (10°–19°), B3 (6°–75°) together with a single crystal of S1 (3°) were stretched at 800 °C. Then, the deformation behaviors, including fracture morphology, crack propagation, and deformation mechanism, were analyzed. Interestingly, these bicrystals show good high-temperature tensile performance, and their deformation behaviors seem to be very anisotropic. The findings indicate that the misorientation disparity in bicrystals primarily determines their deformation coordination capacity and corresponding mechanical performance. Subsequently, the difference in deformation orientation between the two lamellae significantly controls fracture behavior and deformation compatibility. High slip potential and abundant variant choices in γ phases are supposed to be beneficial for deformation capacity improvement. Meanwhile, the deformation potential of ordinary dislocation and superlattice dislocation slip systems in the α2 phase was also examined. Results show that the disparity in dislocation motion ability between γ variants gradually amplifies the advantages of the easy-mode phase in deformation through strain coordination, while mitigating the disadvantages associated with the difficult-mode phase. During further deformation, the relatively low bicrystal misorientation and small deformation capacity differences between the two lamellae determine high deformation coordination and improved performance. Overall, our work reveals that bicrystal deformation initiates at the relatively softer lamellae and proceeds to the harder lamellae, and its final comprehensive performance is determined by the deformation coordination capacity between the two lamellae.