In this research effort, the role of calcium in geopolymers was investigated through a series of syntheses where a high-calcium fly ash was blended with a low-calcium fly ash. Increased calcium content led to accelerated set-up times, increased compressive strength, and increased product formation. Powder X-ray diffraction results showed the majority of that product to be geopolymer framework with only minor contributions from calcium silicate phases. Thermal analysis confirmed the absence of a calcium silicate hydrate phase. Analysis of fly ash dissolution showed that calcium aided in aluminosilicate dissolution and therefore the geopolymerization reaction. While aiding in this reaction, calcium became incorporated into the pore structure of the geopolymer as a counter-balancing cation, according to ion exchange experiments. Thus, geopolymer synthesis with increased calcium content through the use of a high-calcium fly ash under these experimental conditions produced a quick-setting, strong, calcium incorporated geopolymer material.