We report an experimental investigation by electron paramagnetic resonance (EPR) on methyl radical (CH 3 ) observed in γ-ray irradiated high-purity amorphous silicon dioxide (a-SiO 2 ) and in a polycrystalline sample of Melanophlogite, a rare natural form of SiO 2 -clathrate. From the analysis of the EPR spectra we estimate the correlation time of the hindered rotational motion of CH 3 molecules at T=77K in the two different materials. This physical quantity gives a quantitative measure of the freedom of motion of CH 3 molecules trapped in the two solid systems, putting forward relevant information on the properties of the cavities/interstices in which the radicals are confined. In particular, our data suggest that in a-SiO 2 the CH 3 molecules are trapped in interstices with diameter significantly lower than about 5.7Å, which is the size of the smaller cavity involved in the crystalline structure of Melanophlogite.