A silica fume, precipitated silica, metakaolin and siliceous fly ash behavior as constituents of mortars was studied, while mortar samples have been tested for long-term alkali-silica reaction expansion in accordance to the GOST 8269.0 specification. Solid-state ²⁹Si-MAS NMR spectroscopy and thermogravimetric analysis were used to describe Portland cement hydration, supplementary cementitious material pozzolanic reaction and to establish a structure of products of those processes. It was found that long-term test conditions, in contrast to the accelerated test, do not affect the composition of products formed too much, compared to normal conditions. This allows results obtained with long-term test to be expected as more relevant in terms of predicting of supplementary cementitious materials inhibiting properties.