The microstructure of inorganic polymers (IP) formed from fayalite slag was investigated as a function of the composition of different activating solutions. The starting slag was 80 wt% amorphous, and after activation using sodium silicate solutions with varying SiO2/Na2O molar ratios, the amorphous phase dissolved and a binder phase was formed. The morphology of this binder, including the population and size of remnant particles and pores, was dependent on the particular activating solution used, and became denser as the level of silicate rose. Fe-57 Mossbauer spectroscopy revealed that the IP synthesis reaction is combined with the oxidation of Fe2+ from the fayalite slag to Fe3+ in the inorganic polymer binder. The reaction extent varied and could be quantified using the absorption areas of these ions. Data corroborate that the Fe2+ ions in the amorphous part of the fayalite slag and the Fe3+ ions in the new binder phase had an average oxygen-coordination number of 5.