Recent advances of the following four types of asymmetric reactions using organoselenium compounds are reviewed: selenoxide elimination, [2,3]sigmatropic rearrangement via selenoxides, [2,3]sigmatropic rearrangement via selenimides, and [2,3]sigmatropic rearrangement via selenium ylides. In all reactions, the preparation or the intervention of optically active organoselenium compounds having a chiral center on the selenium atom such as selenoxides, selenimides, and selenium ylides is shown to be essential to obtain the chiral organic compounds with high stereoselectivity.