In this study, the molecular dynamics (MD) method was used to study the tensile deformation of polycrystalline γ-TiAl with complex and random grain orientations. Firstly, the tensile deformation was simulated with different average grain sizes (8.60 nm, 6.18 nm, and 4.50 nm) and strain rates (1 × 108 s−1, 5 × 108 s−1, and 1 × 109 s−1). The results show that the peak stress increases with an increase in tensile strain rate, and the peak stress decreases as the grain size decreases, showing an inverse Hall–Petch effect. Upon observing atomic configuration evolution during tensile deformation, it is found that the grain boundary is seriously distorted, which indicates obvious grain boundary sliding occurring. With a further increase in the loading, some dislocations nucleate at the grain boundaries and propagate towards the interior of the grains along the grain boundaries, which demonstrates that dislocation motion is the primary coordination of the mechanical process of the grain boundaries. The dislocation density near the grain boundaries continues to increase, leading to the generation of micro-cracks and eventually causing material failure. Another interesting phenomenon is that the grains rotate, and the specific rotation angle values of each grain are quantitatively calculated. Grain rotation relaxes the stress concentration near the grain boundaries and plays a toughening role. Consequently, the plastic deformation behaviors of polycrystalline γ-TiAl are achieved through the grain boundary mechanical process, that is, grain boundary sliding and grain rotation.