Relatively few studies have characterized basal content and variability of arsenic in polychaetes, despite the potential importance of this element as a pollutant of marine environments. Even less have investigated the chemical speciation of arsenic, occurring as inorganic and organic forms, which reflect a different biological reactivity of the element. In the present paper we integrate existing literature with new data in order to summarize the status quo on arsenic bioaccumulation in polychaetes. We consider species with different trophic habits, phylogenetic relationships, geographic distribution and ecology. Reported data indicate a high variability in arsenic concentration with levels ranging from <1 μg·g−1 to more than 2500 μg·g−1 in different species; some additional species analyzed in this work confirm species-specific characteristics which are not easily explained by biological or ecological factors. The profile of arsenic compounds in polychaetes is different to that of most aquatic organisms. Typically this element occurs in non-toxic organic forms, however several polychaete species have been shown to accumulate relatively toxic molecules and subsequently biotransform them by processes such as methylation. Conclusions from the literature review reveal a complex array of arsenic actions in the environment and suggest a biological role of this element in the life history of some polychaete species.