Epoxy/zirconia hybrid materials were synthesized from a bisphenol-A type epoxy resin, zirconium-tetra-n-propoxide and acetic acid via in situ polymerization. Acetic acid was used to control the hydrolysis and condensation reaction of the zirconium-tetra-n-propoxide. As a result, the zirconia produced by the in situ polymerization was uniformly dispersed into the epoxy matrix on a nano scale or less, and the hybrid materials exhibited an excellent optical transparency. With the increasing zirconia contents, the storage modulus in the rubbery region increased and the peak area of tan delta in the glass transition temperature region decreased. These results indicate that their heat resistance of the hybrid materials could be improved by hybridization with zirconia. Furthermore, the refractive indices of the hybrid materials were significantly improved with the increasing zirconia contents.