Analysis of the torsionangledistribution of poly(vinylidene fluoride) (PVDF) structures at temperatures above its melting point is addressed by combining first principles methods, atomistic simulations and laboratory experiments. Amorphous, α- and β-conformations of PVDF structures have been considered. The results from the atomistic simulations as well as the experiments show that there is a larger probability of the PVDF torsions to be near ±180° at temperatures above the melting point, which is associated more with the β-conformation than the α-conformation.