Polyhedral oligomeric silsesquioxane (POSS) as a special family of organic-inorganic hybrid material has attracted considerable interest in the last few years. The structures of these hybrid materials can be designed easily according to the requirements, which provides great convenience to the research of new materials. In this paper, the synthesis methods of POSS are introduced, and the applications of POSS-based hybrid materials in the fields such as photoelectric materials, flame retardance of polymer and surface modification of the materials are reviewed. It is pointed out that the hybrid materials based on POSS will be widely used and play an important role in the development of material science in the future.