The preparation and characterization of a hybrid material produced by the combination of a modified aldehydic-phenolic resin (MPR) of the Novolac-type with an inorganic oxide is described. Silica sols were embedded within a phenolic resin matrix of a modified Novolac-type. Functionalization of the resin with the introduction of carboxylic groups in the course of the reaction is key to rendering a strong chemical union between the silanol groups of the SiO2 substrate and the COOH groups attached to the MPR resin, producing a core (SiO2)-shell (MPR) structure. The hybrid samples were characterized by spectroscopic techniques (FT-IR and FT-Raman), XRD, TEM, and SEM.