Rapidly developing technology places higher demands on materials, thus the simultaneous improvement of materials’ multiple properties is a hot research topic. In this work, a high-branched silicone epoxy resin (QSiE) was synthesized and applied to the curing system of bisphenol A epoxy resin (DGEBA) for modification investigations. When 6 wt% QSiE was added to the system, the viscosity dropped by 51.8%. The mechanical property testing results indicated that QSiE could significantly enhance the material’s toughness while preserving good rigidity. The impact strength was enhanced by 1.31 times when 6wt% of QSiE was introduced. Additionally, the silicon skeleton in QSiE has low surface energy and low polarizability, which could endow the material with good hydrophobic and dielectric properties. This work provided a new idea for the preparation of high-performance epoxy resin additives, and provided a broad prospect for cutting-edge applications of epoxy resins.