Pulsed plasma polymerization of precursors containing long perfluoroalkyl chains can lead to the formation of structurally well-defined low surface energy films. Greater chemical selectivity and faster deposition rates are found for monomers containing carbon-carbon double bonds compared to their saturated analogues. Critical surface tension values (y(c)) as low as 1.5 mN m(-1) have been achieved, which corresponds to exceptional hydrophobic and oleophobic liquid repellency behavior.