Abstract: Shear modulus is one of important parameters to control the viscous flow, diffusion and structural relaxation of amorphous alloy. Macroscopic shear elasticity determines the change of heat flow. The correlation between the mechanical properties and the heat flow during the structural relaxation and glass transition is one of the important issues to understand the origin of mechanical properties of amorphous alloy. In the framework of the interstitialcy theory, the shear modulus, heat flow and viscosity of Cu_49Hf_42Al_9 amorphous alloy were used to probe the correlation between shear modulus and heat flow. In parallel, evolution of interstitialcy defects concentration was determined by shear modulus in initial and relaxed states. From the perspective of energy, the influence of interstitialcy defects concentration on the thermodynamic properties of amorphous alloy was investigated by activation energy spectrum (AES). Dynamic mechanical analysis (DMA) was used to investigate the dynamic mechanical process of the Cu_49Hf_42Al_9 amorphous alloy. Structural relaxation induced by physical aging and the evolution of internal friction in-situ annealing was discussed. The results demonstrated that interstitialcy theory could accurately describe the relaxation kinetics, shear softening and other phenomena induced by structural relaxation of amorphous alloy. Temperature dependence of the shear modulus in initial and relaxed states can be well predicted by the data of differential scanning calorimetry (DSC). Activation energy spectrum directly reflects the interstitialcy defects concentration, which can be activated per unit activation energy. Structural relaxation leads to a reduction of the defect concentration, which indicates the structure transforms to a more stable state. During the glass transition process, defect concentration rapidly increases, which corresponds to the shear softening accompanied by heat absorption. Structural relaxation induces decrease of both internal friction and atomic mobility of amorphous alloy. However, the atomic mobility is high enough to eliminate the influence of structural relaxation on defect concentration in the supercooled liquid region.