Abstract: Amorphous alloy is a relative new type of glassy materials with short-range ordered and long-range disordered structure, which has unique physical and mechanical properties. A large number of studies have demonstrated that there is an endowment correlation between the mechanical and physical properties of amorphous alloys and their inherent microstructural heterogeneity. In the current research, the (La0.6Ce0.4)65Al10Co25 amorphous alloy is taken as the model alloy. On the basis of the uniaxial tensile tests and stress relaxation experiments, the dynamic evolution law of amorphous alloy during the tensile-stress relaxation process was clarified in the framework of the free volume model. Contributions of aging and rejuvenation effects to the deformation behavior of amorphous alloys in deformation process are effectively separated. The results show that with increasing tensile strain, the amorphous alloys exhibit an elastic phase, a stress-overshoot phase, and a steady-state flow phase, respectively. In the elastic phase, where the strain is small, the rejuvenation due to deformation cannot counteract the effects of aging on the amorphous alloy. While the amorphous alloy is in the inelastic deformation stage, due to the larger strain, the rejuvenation caused by deformation cancels out the influence of aging effect; the steady-state rheological stress of amorphous alloys is determined by the strain rate and is not affected by the aging effect, and the steady-state rheological stress of amorphous alloys tensile curves is the same for different annealing times under the same strain rate. The higher the strain rate, the larger the steady-state rheological stress in the tensile stress-strain curve, the faster the defect concentration increases, and the more obvious the stress overshoot phenomenon.