The purpose of this study was to investigate presence and potential accumulation of cyclic volatile methyl siloxanes (cVMS) in the Arctic environment. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were analyzed in sediment, zooplankton, Atlantic cod (Gadus morhua), shorthorn sculpin (Myxocephalus scorpius), and bearded seal (Erignathus barbatus) collected from the Svalbard archipelago within the European Arctic in July 2009. Highest levels were found for D5 in fish collected from Adventfjorden, with average concentrations of 176 and 531 ng/g lipid in Atlantic cod and shorthorn sculpin, respectively. Decreasing concentration of D5 in sediment collected away from waste water outlet in Adventfjorden indicates that the local settlement of Longyearbyen is a point source to the local aquatic environment. Median biota sediment accumulation factors (BSAFs) calculated for D5 in Adventfjorden were 2.1 and 1.5 for Atlantic cod and shorthorn sculpin, respectively. Biota concentrations of D5 were lower or below detection limits in remote and sparsely populated regions (Kongsfjorden and Liefdefjorden) compared to Adventfjorden. The levels of cVMS were found to be low or below detection limits in bearded seal blubber and indicate a low risk for cVMS accumulation within mammals. Accumulation of cVMS in fish appears to be influenced by local exposure from human settlements within the Arctic.