Composites based on polyvinylidene fluoride filled with barium titanate (PVDF/BT) submicrometric particles were prepared. To uniformly disperse BT particles within PVDF, high-energy ball cryomilling was used. The effect of processing and the presence of BT particles on the structure and morphology of the composites were analyzed by Fourier transformed infrared spectroscopy, X-ray diffraction, differential scanning calorimetry, and atomic force microscopy. In terms of the structure, it can be concluded/stated that after milling the - and -PVDF crystalline phases are reduced, whereas the content in the phase is increased. On the other hand, after film formation, the phase was recovered. It was demonstrated that the milling process is the most important factor to increase the amount of phase, being favored by the presence of BT particles. In terms of the morphology, it was observed that the PVDF lamellar aspect ratio increases with the amount of BT in cryomilled samples processed as films. Besides, the crystallization kinetics is highly affected by the milling process and the presence of BT, being the relative crystallization rate slower with the presence of BT.