The synthesis, characterization and corrosion properties of a novel material, produced by the reaction of silica nanoparticles with a functionalized Phenol-Formaldehyde Resin (PFR), are presented. Carboxylic groups were attached in situ to the PFR skeleton to produce a functionalized resin (PFR-SA), which is then reacted with sol–gel-prepared silica nanoparticles, yielding a novel hybrid (organic/inorganic) material (PFR-SA-nanoSiO2). This hybrid material was characterized by FT-IR, FT-Raman, TGA, DSC, SEM and corrosion tests, whose results showed significant improvement of the thermal properties in comparison with the PFR coating. In addition, the new material was efficient and durable against corrosion of metals, with the anticorrosive performance of PFR-SA and PFR-SA/nanoSiO2 coating films being superior to those of the original PFR coating.