An ionic liquid (IL) was introduced into a vapor-phase free radical polymerization process for the first time. The deposition of poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(1H,1H,2H,2H-perfluorodecyl acrylate) (PPFDA) was studied in the presence of 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) droplets. The polymerization occurred either at the vapor IL interface or within the IL depending on reaction conditions such as the duration of deposition, the stage temperature, and the monomer solubility. A variety of polymeric architectures such as polymer skins that completely encapsulated the droplet, free-standing polymer, and polymer films that float freely on the surface of the IL were formed. The results from this study will facilitate the design of new polymer IL composite materials for use in fuel cell and battery applications.