The mechanical properties of rockfill materials are not only influenced by microscopic factors such as particle morphology and gradation, but also closely related to different loading stress paths. It is of great significance to study the microscopic mechanical properties of rockfill materials under different stress paths for revealing the macroscopic mechanical properties as well as the microscopic deformation and failure mechanisms of rockfill materials. In this paper, based on the results of triaxial tests, a series of numerical triaxial simulation tests under different stress paths were carried out using the discrete element particle flow method, and the deformation, strength change rules, and fine structure evolution mechanism under three stress paths were explored. The results demonstrated that there were significant differences in the effects of stress paths on the stress–strain and strain-volume change characteristics of the rockfill materials. Stress paths exhibited little effect on the strength characteristics. The anisotropy of strong contact number and strong contact force was the microscopic source of macroscopic strength. The contact situation between the particles was the main microscopic factor affecting the macroscopic deformation. The intrinsic mechanism of macroscopic deformation properties could be revealed by the average coordination number and porosity. The stress path affected the growth rate of the number of bond failures and the total number of failures. The relationship between macroscopic mechanical properties and microstructural evolution under different stress paths was also discussed. The findings can provide meaningful insights into the deformation control and stability analysis of rockfill engineering.