Nanostructured Steels Are Expected to Have Enhanced Irradiation Tolerance and Improved Strength. However, They Suffer from Poor Microstructural Stability at Elevated Temperatures. in This Study, Fe–21Cr–5Al–0.026C (Wt%) Kanthal D (KD) Alloy Belonging to a Class of (FeCrAl) Alloys Considered for Accident-Tolerant Fuel Cladding in Light-Water Reactors is Nanostructured using Two Severe Plastic Deformation Techniques of Equal-Channel Angular Pressing (ECAP) and High-Pressure Torsion (HPT), and their Thermal Stability between 500–700 °C is Studied and Compared. ECAP KD is Found to Be Thermally Stable Up to 500 °C, Whereas HPT KD is Unstable at 500 °C. Microstructural Characterization Reveals that ECAP KD Undergoes Recovery at 550 °C and Recrystallization above 600 °C, While HPT KD Shows Continuous Grain Growth after Annealing above 500 °C. Enhanced Thermal Stability of ECAP KD is from Significant Fraction (>50%) of Low-Angle Grain Boundaries (GBs) (Misorientation Angle 2–15°) Stabilizing the Microstructure Due to their Low Mobility. Small Grain Sizes, a High Fraction (>80%) of High-Angle GBs (Misorientation Angle >15°) and Accordingly a Large Amount of Stored GB Energy, serve as the Driving Force for HPT KD to Undergo Grain Growth Instead of Recrystallization Driven by Excess Stored Strain Energy.