To understand the anisotropy dependence of the damage evolution and material removal during the machining process of MgF2 single crystals, nanoscratch tests of MgF2 single crystals with different crystal planes and directions were systematically performed, and surface morphologies of the scratched grooves under different conditions were analyzed. The experimental results indicated that anisotropy considerably affected the damage evolution in the machining process of MgF2 single crystals. A stress field model induced by the scratch was developed by considering the anisotropy, which indicated that during the loading process, median cracks induced by the tensile stress initiated and propagated at the front of the indenter. Lateral cracks induced by tensile stress initiated and propagated on the subsurface during the unloading process. In addition, surface radial cracks induced by the tensile stress were easily generated during the unloading process. The stress change led to the deflection of the propagation direction of lateral cracks. Therefore, the lateral cracks propagated to the workpiece surface, resulting in brittle removal in the form of chunk chips. The plastic deformation parameter indicated that the more the slip systems were activated, the more easily the plastic deformation occurred. The cleavage fracture parameter indicated that the cracks propagated along the activated cleavage planes, and the brittle chunk removal was owing to the subsurface cleavage cracks propagating to the crystal surface. Under the same processing parameters, the scratch of the (001) crystal plane along the