In this study, silicon/shape memory polyurethane (SiO2/SMPU) hybrid sols were prepared using a sol–gel process without water. The structural, mechanical, thermal, and optical properties of the SiO2/SMPU sols were studied. Results indicated that the hybrid sols exhibited uniform size distribution and good dispersion. In addition, the hybrid sols were characterized by transparency and excellent storability even after 6 months when stored in an inert atmosphere. The application of these hybrid sols was also investigated, and it was found that they effectively improve the quality of aramid fibers by enhancing their UV resistance and the binding strength between the coating and the fiber.