Poly(vinylidene fluoride) containing 10% dibutyl sebacate plasticizer, as used in the construction of flexible oil and gas pipelines, has been exposed to raised temperatures for prolonged periods of time, to acid etching and to various tensile deformation regimes. The effects of these treatments on the crystallinity and surface properties of this material have been examined in the light of analytical data obtained by Fourier transform-infrared spectroscopy, differential scanning calorimetry, X-ray diffraction, X-ray photoelectron spectroscopy, goniometry and a variety of microscopy techniques. The results have shown that the molecular organization of this material can be influenced by the adoption of appropriate preconditioning procedures.