Arsenic (As) and antimony (Sb) belong to the same group in the Periodic Table of the Elements and show similar chemical behaviors. Both elements occur widely in the environment and are generally recognized as toxic metalloids. With the development of economy, the pollution of As and Sb becomes a serious environmental issue worldwide and threatens the health of human beings. Microorganisms are well known to play important roles in the transformation and geological cycles of arsenic as well as antimony in nature, especially microbiological oxidation that converts toxic As(III) or Sb(III) to less toxic As(V) or Sb(V). Thus microbial mediated oxidization of As(III) and Sb(III) can be a potential bioremediation for metalloid contamination. This review focuses on the advances of microbial diversity, regulatory mechanism of microbial oxidation of As and Sb and application of arsenite oxidizers and antimonite oxidizers. We try to provide insights into microbial mediated biogeochemical cycles of arsenic and antimony and the development of bioremediation strategies.