2-Methylene-1,3-dioxepane (MDO) was copolymerized with fluoroalkenes (RfCH=CH2) using azobis(isobutyronitrile) AIBN as an initiator. NMR spectroscopy confirmed that the obtained polymers are effectively alternating copolymers of caprolactone and fluoroalkene. Angle resolved XPS of copolymer films revealed that the outer layers have higher CFx:COO ratio relative to the subsurface, indicating that the perfluoroalkyl tails segregate to the air-side, thereby presenting a hydrophobic surface with water contact angle as high as 130 degrees. Blends of this material with polycaprolactone and polycarbonate polymers also form hydrophobic films. In the presence of trifluoroacetic acid, the copolymer undergoes complete. degradation through hydrolysis. (c) 2005 Wiley Periodicals, Inc.