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Nanocomposite optical materials with high refractive index (RI) have been one of the most attractive issues due to their good optical property that can be used in many fields. The method for preparing high RI nanocomposites is to incorporate high RI inorganic nano-building blocks, for example, metal oxides and metal chalcogenide semiconductor nanoparticles into polymer matrices. The general design requirements and synthetic methods of these high RI nanocomposites are discussed in this review. We classify the synthetic methods into two parts: in situ particle generation method and ex situ particle generation method, and all the methods are reviewed. Some optical applications on antireflection coatings, volume holographic recording materials, high RI LED encapsulant materials, photonic band gap materials and other applications are also reviewed. The relevant patents are discussed in this article.