We investigated the effects of increased boron content on the resistance to non-hydrostatic stress-induced (NHSI) local amorphous zones in boron-rich boron carbide (BxC) compounds. Using high pressure Raman spectroscopy, we subjected B4.3C, B6.4C, and B10.4C to pressures up to 50 GPa and monitored their responses. Our results show that higher boron content delays the onset of NHSI local amorphous zone formation, shifting it from 35 GPa in B4.3C to approximately 50 GPa in B10.4C. This enhanced resistance is attributed to a reduction in the formation of the B12(CCC) polytype, which is susceptible to amorphization, and the greater flexibility of B–B–B chains. Furthermore, alternative mechanisms, such as boron vacancy-driven C–C bond formation, provide additional insights into defect-mediated structural changes that may influence the amorphization process. These findings highlight the dual role of boron content and defect mechanisms in improving the structural stability of BxC materials under extreme environments.