The effects of geopolymer binder systems exposed to elevated temperatures are examined. Geopolymers investigated were synthesized from metakaolin, activated by combinations of sodium/potassium silicate and sodium/potassium hydroxide. The specimens were then exposed to temperatures of 800 °C. The factors studied were: (1) calcining temperatures of kaolin; (2) Si/Al ratio of the geopolymer; (3) activator/metakaolin ratio; (4) curing temperature; and (5) alkali cation type. Altogether 30 geopolymer formulations were studied. The samples were subjected to compressive strength, thermogravimetry, and scanning electron microscopy tests. Results showed that Si/Al ratio has a significant influence on elevated temperature exposure deterioration. Lesser strength loss due to elevated temperature exposures were observed in geopolymer with high Si/Al ratios (>1.5). The geopolymer binders activated by potassium-based activators showed an enhanced post-elevated temperature exposure performance compared to sodium-based systems. The optimum calcining temperature of kaolin and curing temperatures for improved temperature performance are also reported.