The article investigates the effects of long term environmental aging on thermal and mechanical properties of epoxy-silica hybrids. These nanostructured materials, prepared by non-aqueous sol-gel process and in situ generation of nanosilica during epoxy curing at room temperature, present the potential to be used as cold-cured adhesives for civil engineering and Cultural Heritage applications. A specifically developed conditioning procedure for these cold-cured nanostructured materials was applied before moisture/water absorption tests. The work evidenced the superior durability of the studied epoxy-silica hybrid, which kept its performances in severe, but realistic, environmental conditions with respect to traditional epoxy adhesives. The reduction in the glass transition temperature and mechanical properties of the studied epoxy-silica hybrid, observed in the first weeks of environmental aging, was followed by a significant recovery. This was attributed to two concomitant phenomena: the reactivation of the incomplete curing reactions in the epoxy domains and the continuation of the condensation reactions in the siloxane domains activated by the absorbed water. Finally, the Fickian behavior, presented by the studied epoxy-silica hybrid, was used as an indirect indication of the homogeneity of achieved microstructure, with well dispersed silica nanostructures in the epoxy network. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40093.