Poly(vinylidene fluoride) (PVDF) and PVDF-based copolymers with trifluoroethylene (PVDF-TrFE) have attracted considerable academic and industrial interest due to their ferroelectric properties, which are only presented in very few polymers. However, the underlying fundamentals of molecular ordering and induced polarizations are complex and not fully understood. Herein, PVDF, PVDF-TrFE and their blends, prepared using melt extrusion and hot pressing, have been selected to obtain controlled case studies with well-defined chain ordering and microstructures. Impedance analysis and terahertz time-domain spectroscopy are exploited to investigate electric polarization in PVDF-based polymers at different length scales. The extruded ferroelectric films show in-plane chain orientation and higher domain wall density compared to hot pressed films with randomly-distributed polymer chains, which favors the polarization at low frequencies (Hz to MHz), as concluded from the higher dielectric constants and more prominent high electric field polarization switching features. However, the domain walls cannot respond at high frequencies, which leads to lower dielectric constants in the extruded films at THz frequencies
