Previous experiments have revealed that the controllable introduction of structural gradients in metallic glasses (MGs) can endow the materials with extra plasticity due to the gradient-induced deflection of shear bands. However, the relation between the spatial structural gradient and the initiation of shear band deflection remains unclear. The current study has been focused on investigating the relationship between the improved mechanical properties of MGs and structural gradients specified by the distribution of the intrinsic free volume. Molecular dynamics (MD) simulations are firstly performed on homogeneous MG models containing various initial free volume values, showing that the shear band angle increases with decreasing free volume under uniaxial compression, whereas higher shear band angle is observed under uniaxial tension with increasing free volume. Based on the asymmetric behaviors of MGs under compression and tension, a theoretical model is developed to quantitatively characterize the influence of free volume on the mechanical response of MGs, which incorporates a failure criterion based on free volume generation during external loadings. The model can be further utilized to interpret and predict the fracture strain, shear band angle, maximum stress, and fracture surface morphology of gradient structured MGs in both simulations and experiments. The relationship between free volume gradient and shear band deflection induced extra plasticity established in this study provides valuable guidance for the structural design of MGs with enhanced mechanical properties.