Resveratrol (RES) is a naturally occurring product with numerous biological activities. Despite its potential benefits, its use is limited due to its low aqueous stability and solubility in its native form. The porous sol–gel silica materials which are able to entrap different organic molecules represent new studied release carriers. The aim of this work was to generate a solid matrix to encapsulate RES ensuring protection, increased solubility and release in solutions. A non-toxic ingredient, namely β-cyclodextrin (β-CD), able to form inclusion complexes (ICs) with RES has been used. Ecological formulations have been processed by entrapping the RES containing ICs in silica matrices obtained from a silica colloidal sol by the aqueous route of the sol–gel method. Characterization methods (DSC, FTIR, UV–Vis, fluorescence studies, SEM) have evidenced the presence of RES–β-CD inclusion complex in the silica powder, RES stability in the matrix and its release in aqueous and organic solutions, and the morphology of the carrier. An evaluation of the antioxidant activity of RES in the present formulation was performed by the chemiluminescence assay and RES release profile in aqueous solutions was obtained by HPLC–MS. The resulted materials can find applications in different domains.