The kinetics of the isothermal crystallization from the melt of α- and γ-poly(vinylidene fluoride), PVDF, and the corresponding melting behaviour has been investigated. The crystallization kinetics was evaluated on the basis of the theory of Avrami. The variation of the microstructure of the samples crystallized at different temperatures was monitored along time by optical microscopy with polarized light. The correlation between microstructure and kinetic parameters allows tailoring the microstructure of the polymer by choosing specific crystallization conditions. Infrared spectroscopy and Raman spectroscopy show the appearance of the γ-phase for higher crystallization temperatures.