This paper presents the results of a study on the effect of elevated temperatures on geopolymers manufactured using metakaolin and fly ash of various mixture proportions. Both types of geopolymers (metakaolin and fly ash) were synthesized with sodium silicate and potassium hydroxide solutions. The strength of the fly ash-based geopolymer increased after exposure to elevated temperatures (800 °C). However, the strength of the corresponding metakaolin-based geopolymer decreased after similar exposure. Both types of geopolymers were subjected to thermogravimetric, scanning electron microscopy and mercury intrusion porosimetry tests. The paper concludes that the fly ash-based geopolymers have large numbers of small pores which facilitate the escape of moisture when heated, thus causing minimal damage to the geopolymer matrix. On the other hand, metakaolin geopolymers do not possess such pore distribution structures. The strength increase in fly ash geopolymers is also partly attributed to the sintering reactions of un-reacted fly ash particles.