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Crystalline Langmuir–Blodgett copolymer films of vinylidene fluoride with trifluoroethylene (70%:30% and 80%:20%) absorb water. Water absorption is accompanied by film swelling, as indicated by an increase in lattice spacing, sometimes by as much as 5%. This water absorption, between 0 and 40 °C, is a result of intercalation or occupation of interstitial sites between the layers of the film, not just water molecules filling voids and defect sites alone. An increase in the film capacitance is observed, although the polymer chains retain all trans configuration of the ferroelectric phase. © 2004 American Institute of Physics.