The requirements regarding the weight and capacity reduction of neutron shielding materials have become an urgent issue for advanced nuclear facilities and plants. An epoxy-based neutron shielding material with high-temperature stability and good neutron irradiation resistance was designed in this paper to solve the above issue. Aminophenol trifunctional epoxy resin (AFG-90H) was compounded with samarium oxide (Sm2O3) by means of an ultrasonic-assisted method and the compatibility of Sm2O3 with the AFG-90H matrix was improved by 3-aminopropyltriethoxysilane (APTES) surface modification. Fabricated Sm2O3-APTES/AFG-90H composites exhibited improved thermal stability, glass transition temperature and Young’s modulus with increased Sm2O3-APTES content. Neutronics calculation results show that the neutron permeability of 2 mm-thick 30 wt% Sm2O3-APTES/AFG-90H was 98.9% higher than that of the AFG-90H matrix under the irradiation of the thermal neutron source. The results show that the proper addition range of Sm2O3-APTES is between 20% and 25%. The Sm2O3-APTES/AFG-90H composite is a promising neutron shielding material for advanced nuclear system.