In recent years, methylated thioarsenicals have been widely detected in various biological and environmental matrices, suggesting their broad involvement and biological importance in arsenic metabolism. However, very little is known about the formation mechanism of methylated thioarsenicals and the relation between arsenic methylation and thiolation processes. It is timely and necessary to summarize and synthesize the reported information on thiolated arsenicals for an improved understanding of arsenic thiolation. To this end, we examined the proposed formation pathways of methylated oxoarsenicals and thioarsenicals from a chemical perspective and proposed a novel arsenic metabolic scheme, in which arsenic thiolation is integrated with methylation (instead of being separated from methylation as currently reported). We suggest in the new scheme that protein-bound pentavalent arsenicals are critical intermediates that connect methylation and thiolation, with protein binding of pentavalent methylated thioarsenical being a key step for arsenic thiolation. This informative review on arsenic thiolation from the chemical perspective will be helpful to better understand the arsenic metabolism at the molecular level and the toxicological effects of arsenic species.