This study investigated the degradation mechanisms of SiC-MgAl2O4 refractory materials in a bench-scale entrained flow gasifier. Layered degradation and protective SiO2 formation on SiC aggregates were observed by macroscopic, microscopic, phase analysis, and thermodynamic calculations. A comparative investigation of erosion rates revealed that SiC-MgAl2O4 materials located away from the burner had an unusually low erosion rate of 0.0017 mm/h, which was significantly lower than that reported in their counterparts situated near the burner (0.0167 mm/h). This performance surpassed even that of high-chrome refractory materials positioned at a similar distance from the burner. The findings underscore the remarkable durability of SiC-MgAl2O4, demonstrating its significant potential as a sustainable and chrome-free alternative for application in harsh gasification conditions. The environment-specific degradation patterns, characterized by the formation of mullite and cordierite, revealed the complex interaction between refractory materials and gasification environments. This understanding offers valuable insights that can inform the development and implementation of chrome-free refractory materials under industrial gasification conditions.