Water soluble gold nanoparticles, obtained by the reduction of the gold (III) chloride with sodium borohydride in the presence of citric acid or thioctic acid, were covered with a paramagnetic silica layer using the Stober method, yielding a hybrid metallic-inorganic nanomaterial (gold nanoparticles, with an average size of 5 nm, embedded into silica nanoparticles, with an average size of 100 nm). The paramagnetic silica layer was formed by copolymerization of a paramagnetic silica precursor (derived from 3-aminopropyltrimethoxysilane) with tetramethyorthosilicate. The paramagnetic silica precursor was obtained by coupling 3-aminopropyltrimethoxysilane with 3-carboxy-proxyl free radical. TEM pictures show that each silica nanoparticle of about 100 nm in size embedded about 10 gold nanoparticles. These hybrid nanoparticles are quite stable and exhibit the expected paramagnetic characteristics, as seen by electron paramagnetic resonance. The accessibility of methanol through the silica layer was also studied. Depending on the capping ligands of the gold nanoparticles (citric or thioctic acid), different silica networks are formed, as seen by the mobility of the spin-label inside the silica layer. The EPR spectra showed that the paramagnetic silica layer is very robust and the mobility of the spin-probe inside the silica layer is very little affected by methanol. However, if spin-labeled thioctic acid protected gold nanoparticles were used in the material synthesis, the mobility of the spins attached to the gold surface is quite high in the presence of methanol, while the spins embedded into the silica layer remains immobilized.