Sodium-based fly ash geopolymers show great fire resistance potential and commercial advantage for structural applications. Hence, in current research, tailoring of sodium-based geopolymer mix design without changing the fly ash source has been studied. It was found that a wide variety of residual compressive strength ranging from significant reduction (~80%) to maintaining significant enhancement (~150%) after being exposed to 900 °C was observed. The contributory mechanisms were discovered by investigating their chemical stability, pore structures, volume stability, and strength endurance prior to and after exposure to high-temperature using different microstructure characterization techniques including XRD, FTIR, MIP, dilatometry, and SEM. Crack formation due to moisture migration, pore shrinkage, and re-crystallization of nepheline adversely affected compressive strength. Matrix densification due to shrinkage of pore and stronger inter-particle bonding due to viscous sintering, favored compressive strength gain. This work discusses at length these competing mechanisms influencing the residual compressive strength.