There are indications on that the initial setting time is dependent on the relative ratio of Na2O to SiO2 when sodium silicate solutions (Na2SiO3) are used for the alkali-activation of ground granulated blast-furnace slag (GGBS). One possible reason for this is that the ratio (called modulus) not only influences the pH but also the viscosity of the solution. The viscosity is, in turn dependent on the structures in the liquid. Therefore, we have investigated the structure of sodium silicate solutions of different moduli by infrared spectroscopy (IR) and silicon nuclear magnetic resonance (Si-29-NMR). The results, which show that the silica configuration is highly dependent on the modulus, will be discussed in relation to the initial setting time of corresponding measurements on GGBS hydration