Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectroscopy was used to monitor the in situ sorption of sodium metasilicate from aqueous solution onto synthesized magnetite and maghemite particles in the pH range 10.8-7.0 using silicate concentrations between 0.1 mM and 5 mM. The spectral data showed that both pH and silicate concentration had great influence on the interfacial reaction between soluble silicate and the iron oxide surfaces, regarding the amount adsorbed per unit mass of iron oxide and the surface species formed. A pH dependent sorption of silicate on iron oxides was observed, implying that a maximum sorption took place in the pH range of 9.5 - 7.0. All experiments showed a fast initial increase in the absorption intensity followed by a slower sorption stage which was strongly dependent on the concentration of silicate in solution and the pH value. The amount of sorption onto magnetite was 3 to 5 times larger than onto maghemite, but there was no significant difference in the line shape of corresponding absorption bands. At pH 8.5 and low concentration (≤ 0.1 mM), the silicate monomers dominate in solution and on the iron oxide surface also monomeric species were dominating as evident from the infrared band at 950 cm-1. However, at higher concentration (0.4-5.0 mM), the dominating absorption band at about 1000 cm-1 shifted to higher frequency during the sorption indicating that oligomeric surface silicate species were formed on the iron oxide surface. Desorption of silicate from the surface of the iron oxides was easier to accomplish at low silicate concentration, whilst the highest concentration showed a comparatively low relative amount of desorbed silicate, suggesting that polymerized species had a stronger affinity for the iron oxide surface as compared to monomeric species.