New silica-based particles embedding iron were synthesized following a freeze-drying-assisted sol–gel route. The samples were preliminary characterized in view of potential applications as theranostic magnetic resonance imaging (MRI) contrast agents and for hyperthermia treatment. The structural changes induced by iron addition were studied by X-ray diffraction, Fourier transform infrared and electron paramagnetic resonance spectroscopies. The addition of Fe2O3 impedes the SiO2 crystallization denoting that iron plays, in this case, the role of a glass network stabilizer. The composition on surface and nearby was analyzed by X-ray photoelectron spectroscopy and energy dispersive X-ray spectroscopy both before and after samples immersion in simulated body fluid. The results suggest the nominal composition with 5 mol% Fe2O3 added to 0.7SiO2∙0.3Na2O matrix of interest for further investigations as potential MRI contrast agent and hyperthermia vector.