Gas/vapor-deposition polymerization (GDP) of vinyl monomer is expected to exhibit a unique polyinerization behavior different from its polymerization in the liquid phase. Free-radical GDP of 2,2,3,3,3-pentafluoropropyl methacrylate (FMA) was carried out with a conventional free-radical initiator (azobisisobutyronitrile) on substrate surfaces. A linear relationship between the number-average molecular weight and polymer yield was observed, and the consecutive copolymerization of methyl methacrylate (MMA) and FMA led to the formation of block copolymer P(MMA-block-FMA). These results suggested that the GDP process on substrate surfaces has a living nature. During the process, the active species at growing chain ends may be immobilized on the deposit surface and restricted from the chain-transfer reactions, resulting in a continuation of the propagation reaction. The GDP on substrate surfaces is therefore a physically controlled polymerization process. (C) 2004 Wiley Periodicals, Inc.