Unsaturated polycarbosilanes composed of silicon and conjugated groups have been ideal and promising candidate for semiconductors, organic electroluminescence, ceramic precursors, heat-resistant materials and photovoltaic materials, due to their high thermal stability, good solubility, easy processability and low toxicity attributes. Therefore, unsaturated polycarbosilanes have long been the research focus in the field of silicone materials. This paper firstly summarizes the recent research progress and synthesis methods of unsaturated polycarbosilanes, including hydrosilylation reaction, Suzuki-Heck reaction and Wittig reaction. Then the application of unsaturated polycarbosilanes in photovoltaic and organic electroluminescence, are introduced.