Low-calcium fly ash-based geopolymer concrete is generally reported to be less vulnerable to alkali-silica reaction (ASR) than conventional ordinary Portland cement concrete. However, the lack of understanding of pore solution composition of the low-calcium fly ash-based geopolymer limits the investigation of the underlying mechanisms for the low ASR-induced expansion in the geopolymer concrete. This study presents a systematic investigation of the pore solution composition of a low-calcium fly ash-based geopolymer over a period of one year. The results show that the pore solution of the fly ash geopolymer is mainly composed of alkali ions, silicates, and aluminosilicates species. The lower expansion of the geopolymer concrete in the current study is most probably due to the insufficient alkalinity in the geopolymer pore solution as the hydroxide ions are largely consumed for the fly ash dissolution.