This paper presents the plasma polymerization of poly(hexafluorobutyl acrylate) (PHFBA) thin films on different substrates in an RF plasma reactor with an outer planar electrode. This reactor configuration allows large area uniformity and fast processing times. Deposition rates of up to 60 nm min-1 were observed. The influence of plasma power and substrate temperature on the deposition rate, structure and wettability of the as-deposited films was investigated. It was observed that better hydrophobicity was obtained at high plasma power and in low temperature conditions. PHFBA thin films deposited on electrospun poly(acrylonitrile) fiber mats under such conditions resulted in superhydrophobic surfaces with contact angle values greater than 150. In vitro cell studies using human epithelial cells demonstrated the non-Toxic nature of the plasma-polymerized PHFBA films.