Isolated nanometric particles (D < 30 nm) of γ-Fe2O3 in a silica matrix have been prepared by heating at 400 °C the gel formed in the hydrolysis of an ethanol solution of Fe(NO3)3·9H2O and tetraethylorthosilicate (TEOS). However, when FeCl3·6H2O was used as precursor, well-developed hematite particles were obtained in the final composite. This different behavior was already manifest in the initial gels. Thus, the gel obtained from iron nitrate salt shows a compact appearance as a result of its higher degree of network connectivity (polymeric gel) whereas the one from the iron chloride appears more loose and highly hygroscopic (colloidal gel). In addition, small superparamagnetic nuclei are formed during the hydrolysis and condensation of the gel obtained from the iron nitrate salt. The γ-Fe2O3 nanoparticle formation takes place through a reduction−oxidation reaction which occurs during the burning of the organic species trapped inside the gel pore. The growth mechanism of the γ-Fe2O3 nanoparticles in the ...