Poly(vinylidene fluoride) (PVF2) produces a thermoreversible gel with the important solvent, ethylene carbonate, which is used as a dispersing medium in a lithium ion battery. This is evidenced from the fibrillar network morphology and reversible first-order phase transition of the gels. The invariance of the storage and loss modulus with frequency at lower temperatures (<= 110 degrees C) and the existence of a crossover point between them at higher temperatures further supports thermoreversible gel formation in the system. Solvent subtracted FTIR spectra of the gels indicate formation of a beta polymorph, which is retained even after drying using cyclohexane as a guest solvent. The wide-angle x-ray scattering (WAXS) diffractogram of the dried gel also indicates formation of the piezoelectric beta polymorph, giving a first time report of thermoreversible piezoelectric gel formation. The temperature-concentration phase diagram in conjunction with Tamman's plot indicates the presence of a polymer-solvent molecular compound whose stoichiometry is around 1.2 solvent molecules/monomer unit. The presence of eutectic and metatectic transitions in the PVF2-ethylene carbonate (EC) system is also evidenced from the phase diagram. Time-resolved X-ray diffraction patterns also show a new peak at q = 13.15 nm(-1) which is assigned to the molecular compound on the basis of a possible crystalline lattice. Molecular modeling using molecular mechanics calculations with the MMX program supports polymer-solvent complex formation. It also indicates that electrostatic and H-bonding forces are operating side by side on the carbon skeleton fixing the all trans chain conformation of beta PVF2 in the gel.