PVDF exhibits ferroelectric, pyroelectric, and dielectric properties as a function of its unique crystalline phases, namely α, β, γ, δ, and ε. Of these, the β crystalline phase shows unique electrical and mechanical properties due to its highly ordered crystalline lamellae and is of industrial interest. Electrospinning is a unique technique to produce long flawless fibers for various applications. In this study, several MgTiO₃–PVDF composites were prepared by the electrospinning and solution-casting methods. The objective of this was to examine the combined effect of a popular, low-loss ceramic dielectric like MgTiO₃ and a high-dielectric polymer like PVDF in a new architecture. The effect of the filler dispersion on the microstructure, phase transition, and mechanical and electrical properties of the MgTiO₃/PVDF composites was investigated in the frequency range of 100 Hz–100 MHz and at 10 GHz. The dynamic mechanical properties of the composites (1–100 Hz) have also been examined. These polymer composites composed of highly crystalline PVDF nanofibers and MgTiO₃ appear to have promising dielectric properties distinctly different from their constituent components.