This contribution investigates the polymorphism evolution of poly(vinylidene fluoride) (PVDF) mats prepared through electrospinning solutions of PVDF in pure N, N-dimethylformamide (DMF) and DMF/acetone mixtures with different weight ratios. To explore the influence of the process- as well as solution-related parameters, electrospun webs were characterized with respect to their morphologies and polymorphism features using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and Fourier transfer infrared spectroscopy (FTIR) techniques. Among various processing parameters, rotation of the collecting drum was found to have a pivotal role in the enhancement of beta phase formation. Furthermore, dielectric tests were conducted to disclose the influence of aforementioned parameters on dielectric constant, remnant polarization and coercive field of the mats. It was confirmed that the ferroelectric properties of PVDF electrospun mats can be dominantly controlled by orienting fibers in the produced web using a drum collector.