Arsenic (As) poses a risk to the human health in excess exposure and microbes play an important role in the toxicity of As. Arsenic methylation mediated by microbes is a key driver of As toxicity in the environment and this paper reviews the role of microbial arsenic methylation and volatilization in the biogeochemical cycle of arsenic. In specific, little is presently known about the molecular mechanism and gene characterization of arsenic methylation. The uptake of methylated arsenic in plants is influenced by microbial arsenic methylation in soil, thus enhancing the volatilization of methylated arsenic is a potential mitigation point for arsenic mobility and toxicity in the environment. On the other hand, the potential risk of methylated arsenic on organisms is also discussed. And the directions for future research, theoretical reference for the control and remediation of arsenic methylation, are presented.