A straightforward scalable method for synthesizing β-poly (vinylidene fluoride) polymer foam from a sugar template has been used. A characteristic β-phase of the foam was confirmed by infrared and micro-Raman spectroscopy with significant enhancement observed after poling. The electrical polarization of the foam revealed a ferroelectric nature with dielectric strength higher than 30 kV/cm which is close to the commercial value. Poled samples had a dielectric constant of 5.5, higher than the value of the unpoled sample (3.05). These values appear stable over the low-frequency range from 1 kHz to 1 MHz. Significant reverse behavior was observed at higher frequencies from 300 GHz to 3 THz frequencies. It was found that the open-cell foam with a porosity of 88% has the lowest dielectric constant value (1.07 at 1.8 THz, reaching 1.04 at 2.9 THz) compared to the foam with 20% porosity (2.17 at 1 THz, reaching 1.83 at 3 THz). Furthermore, the Maxwell Garnett model, in conjunction with THz imaging, confirmed the impact of porosity on dielectric properties. These findings pave the way for the efficient fabrication of ferroelectric porous polymer structures that can be used in dielectric switching at the kHz–THz frequency range.