In concrete structures, the reaction of certain siliceous aggregates with the highly alkaline concrete pore solution produces an alkali-silicate gel that can absorb water and expand. This reaction can lead to expansion, cracking, increased permeability, and decreased strength of the concrete. Massive concrete structures, such as dams, are particularly susceptible to the damage caused by the alkali-silica reaction because of the availability of water and because massive gravity dams usually do not contain steel reinforcement to restrain the expansion. Both the cement hydration products and alkali-silica reaction products are extremely sensitive to humidity. Consequently, characterization techniques that require high vacuum or drying, as many existing techniques do, are not particularly appropriate for the study of the alkali-silica reaction because artefacts are introduced. Environmental scanning electron micrographs and scanning electron micrographs with energy dispersive X-ray analysis results demonstrate the effect of drying on the morphology and chemical composition of the alkali-silicate reaction gel. Thus, the impetus for this research was the need to observe and characterize the alkali-silica reaction and its gel product on a microscopic level in a wet environment (i.e. without introducing artefacts due to drying). Only soft X-ray transmission microscopy provides the required high spatial resolution needed to observe the reaction process in situ. The alkali-silica reaction can be observed over time, in a wet condition, and at normal pressures, features unavailable with most other high resolution techniques. Soft X-rays also reveal information on the internal structure of the sample. The purpose of this paper is to present research, obtained using transmission soft X-ray microscopy, on the effect of concrete pore solution cations, namely sodium and calcium, on the product formed as a result of alkali attack. Alkali-silicate reaction (ASR) gel was obtained from the FURNAS Dam in Minas Gerais, Brazil. Images of the ASR gel in sodium hydroxide indicated dissolution and repolymerization of the silicate into a less dense form, demonstrating the expansive nature of the gel when exposed to alkalis. In the calcium hydroxide solution, ASR gel, silica fume, and chemical grade silica gel each reacted with the calcium ions in solution to produce a calcium silicate hydrate precursor with a lathlike, branching morphology. The distinctive spherulitic microstructure formed during this reaction was identified as the 'sheaf of wheat' morphology, previously described in the literature. In addition, the development of the sheaf of wheat morphology was documented over time. These results suggest that of the cations studied in this investigation, it is the alkalis in concrete pore solution that produce the expansive ASR gel, while reaction with calcium ions does not result in expansion or damage to the concrete structure. More broadly, these results demonstrate the advantage of transmission soft X-ray microscopy for the study of the alkali-silica reaction, indicating the value of this technique for further studies in concrete technology.