A method with good precision has been developed to quantitatively measure the degree of alpha-, beta-, and,gamma crystallinity in poly(vinylidene fluoride) (PVDF) by means of infrared spectroscopy. The phase composition of solution-deposited PVDF films was found to be strongly influenced by the presence of hydrophilic residues on the silicon substrate, the relative humidity present at film deposition, the spatial position on the substrate, and the thermal treatment of the deposited film. Films produced on pristine surfaces gave predominantly alpha-phase PVDF, but when a layer of polar solvent (acetone or methanol) remained on the surface, the films produced were predominantly gamma phase. Higher humidity promoted a higher fraction of gamma crystallinity in the solution-deposited PVDF films. Solution-cast films had highly variable composition across the substrate, whereas spin-cast films were uniform. High-temperature annealing of PVDF films normally converts the polymer to the gamma phase, but annealing the film while still attached to the silicon substrate inhibited this phase transformation. Low-temperature annealing of freestanding films led to a previously unreported thermal event in the DSC, a premelting process that is a kinetic event, assigned to a crystalline relaxation. Higher-temperature annealing gave a double endotherm, assigned to melting of different-sized crystalline domains. (C) 2003 Wiley Periodicals, Inc.