In this study, hybrid materials based on epoxy resin were prepared as transparent self-supported films by a sol-gel process. 4,4'-Diaminodiphenylmethane or oligomeric epoxy resin were used as precursors, which were conveniently functionalized with trialkoxysilanes as end-groups. The effect of the introduction of poly (dimethylsiloxane) was also investigated. The hybrid films showed good thermal stability, a nondefined glass transition temperature, and a dense morphology without phase segregation. The tendency to a flat surface could be observed by atomic force microscopy. The hybrid films also showed good performance as coatings for glass plates, with an improved hydrophobic character in comparison to neat epoxy resin.