Communication: The atom-transfer radical polymerization (ATRP) of acrylates in 1-butyl-3-methylimidazolium hexafluorophosphate was investigated. The solubility of the acrylates in the ionic liquid depends on the substituent. The homogeneous polymerization of methyl acrylate gives polymers with (M) over bar (n) close to the calculated value and relatively narrow polydispersity. In heterogeneous polymerizations of higher acrylates, with the catalyst present in the ionic liquid phase, deviations from ideal behavior are observed although the polymerization of butyl acrylate approaches the conditions of a controlled polymerization.