The kinetics of the isothermal crystallization from the melt at different crystallization temperatures and the melting behaviour of Poly(vinylidene fluoride) (PVDF) in the alpha phase has been investigated. The variation of the microstructure of the samples crystallized at different temperatures was monitored with time by Optical Microscopy. The correlation between microstructure and kinetic parameters allows the tailoring of the microstructure by choosing the crystallization conditions of the samples. Raman and Infrared Transmission Spectroscopy also show the appearance of the γ-phase for higher crystallization temperatures. The influence of the crystallization kinetics on the degree of crystallinity of the samples will be also presented and discussed. © 2007 Materials Research Society.