Microbial communities at six fumarole fields on Sierra Negra and Alcedo volcanoes in the Galápagos Islands were examined to test how extreme geochemical conditions affect microbial biodiversity. The geologic substrates consist of basalt and rhyolite with varying amounts of alteration and sulfur precipitates. Collected samples of substrates varied in pH from 0-6, and substrate temperatures were within the mesophilic, thermophilic, and hyperthermophilic temperature ranges. Terminal restriction fragment length polymorphism (T-RFLP) analyses were done to assess the relationship of communities to each other as a function of geologic substrate, pH, and temperature. Comparative analyses of community diversity define two distinct clusters showing that the relationship between spatially separated microbial communities at the fumaroles is most influenced by the pH of the local environment.