The manipulation of crystal superstructure and polymorphism of poly(vinylidene fluoride) (PVDF) are of great technical importance to expand its applications in flexible electronics. In this work, strong ion-dipole interaction via the introduction of cetyltrimethylammonium bromide (CTAB) in PVDF induced zig-zag conformers [i.e., the precursor nuclei of beta/gamma folded chain crystals (FCCs)]. Meanwhile, favorable conditions (i.e., high temperature and high pressure) for the pseudohexagonal (hex) paraelectric (PE) phase with gauche conformers [i.e., the precursor nuclei of extended-chain crystals (ECCs)] are purposely chosen to study whether there is any synergy between the ion-dipole interaction and ECCs. It is interesting to find that the high pressure/high temperature hex PE phase can be substantially affected by the strong ion-dipole interaction between PVDF and CTAB. For the neat PVDF melt, most hexagonal folded-chain (h-FC) nuclei ultimately lead to major beta/gamma ECCs. For the PVDF melt with 5 wt% CTAB, the beta/gamma FC nuclei induced by the strong ion-dipole interaction compete with the h-FC nuclei at the initial nucleation stage. The beta/gamma FC nuclei are found to be more kinetically favorable in the beginning under a high pressure, leading to major beta/gamma FCCs and minor beta/gamma ECCs. Furthermore, compared to neat PVDF, addition of 5 wt% CTAB resulted in ECCs of a thinner lamellar thickness. Finally, this new understanding leads to a modified T-P phase diagram, in which the kinetically favorable area for alpha/beta/gamma FC nucleation expands to higher temperatures because of the strong ion-dipole interaction.