In this work, a novel nonaqueous sol method for preparing 3-methacryloxypropyltrimethoxysilane modified nano-SiO2(MPS-SiO2) in N, N-dimethylformamide (DMF) substituting alcoholic solvents was developed, and epoxy acrylate resins (EA) based on novolac epoxy resin (EP) were prepared. Epoxy acrylate copolymers (EPAc/SiO2) with core/shell structure were prepared by one-step in-situ solution polymerization of EA, acrylic monomers and a certain amount of modified silica sol as core. Epoxy acrylate based polyurethane composites/SiO2(EPUAs/SiO2) were finally obtained by curing action among as prepared EPAc/SiO2, isocyanate and anhydride curing agent. The obtained EA and MPS-SiO2 were also characterized using Fourier transform infrared spectroscopy (FTIR), H-1 nuclear magnetic resonance spectra (H-1 NMR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy(XPS), and surface contact angle analysis(CA). Microstructures of MPS-SiO2 and EPAc/SiO(2)in DMF were observed by transmission electron microscope (TEM). Furthermore, the influence of MPS-SiO(2)on the properties of EPUAs/SiO2 including fracture surface morphology, thermal stability, glass transition temperature (Tg), tensile strength, elongation at break, cross-linking density, shore hardness, water absorption, etc. were also investigated. The results demonstrate that colloidal MPS-SiO2 with DMF as solvent can be directly added into polyurethane system and has industrial application value, EPAc/SiO2 with core-shell morphologies have good individual dispersion in DMF, and incorporating MPS-SiO2 into EPUAs/SiO2 greatly enhances physico-chemical properties of EPUAs/SiO2 composites. (C) 2014 Elsevier B. V. All rights reserved.