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Organic–inorganic hybrid composites have received much attention of scientists in the recent years due to the notable improvement of thermal properties without using of organic or inorganic nanoparticles. Hence, we have developed a facile strategy to prepare a 3D hybrid network based on silane materials and novolac resin via sol–gel process. At first step, novolac resin was prepared by general procedure with appropriate thermal properties and then modified with (3-chloropropyl)triethoxysilane (CPTES) to form MNR. In second step, to cure MNR and prepare hybrid composite structures, general amine-cured system and sol–gel process were applied to prepare MNH and MNSG samples, respectively. XRD analysis was used to support the formation of silane networks in hybrid samples. Investigation of thermal properties by DSC and TGA showed that cured samples had much higher thermal stability and char yield with respect to novolac and modified resin (MNR) originated from formation of 3D Si–O–Si network. Presented method limited some disadvantages of using nanoparticles such as aggregation and poor distribution. Such hybrid composites with high thermal stability have potential applications in advanced fields such industrial molds, coatings, adhesives and composites. [ABSTRACT FROM AUTHOR]