The crystal chemistry of a number of Fe-Si systems (Si/Fe 0-4, pH 3-10) was investigated by combining local scale spectroscopic methods (EXAFS, FTIR and NMR) and at the semi local scale (SAXS). The Fe clusters within the precipitates have two growth regimes depending on the Si/Fe ratio: the growth is three and two dimensional for Si/Fe fl and Si/Fe ≤ 1 respectively. The presence of Fe-O-Si bonds within the precipitated phases has been demonstrated. Their formation and relative proportion was found to be very dependent on the pH and Si concentration The size of silica domains within the precipitates was shown to increase with increasing Si/Fe and/or decreasing pH. The high fractal dimension (Df) of the aggregates is attributed to the presence of the SiO4 ligands, but the evolution of Df linearly depends on the polymerization state of iron.