Poly(vinylidene fluoride) (PVF2)-camphor systems have been investigated in concentrations ranging from W-PVF2 = 0 to 1 (w/w). The temperature-concentration phase diagram suggests the formation of two different polymer-solvent compounds of an incongruently melting type (C-1 and C-2), a eutectic transition, and a metatectic transition. The data related to the melting enthalpy of the different first-order events provide one with stoichiometries of 1/2 and 1/4 for compound C, and compound C2, respectively (number of camphor molecules per PVF2 monomer). Time-resolved X-ray experiments carried out as a function of temperature also support the existence of two different compounds. The optical microscopy shows an abrupt change of texture with increasing temperature. The morphology as observed from SEM after drying under vacuum shows tubular, porous structures for concentration below the stoichiometric composition of compound C2 and the appearance of spherulites above.