In this paper, we report on the development of an organic-inorganic hybrid multiferroic material based on polyvinylidene fluoride (PVDF) and nanostructured aluminium iron garnet (Al3Fe5O12) that is found to exhibit enhanced coupling between ferroelectric and magnetic orderings at room temperature. In addition to the promising multiferroic feature, PVDF-based multiferroics can display a remarkable degree of flexibility, giving increased advantage in device fabrication. With a view of extending the synthesis of the PVDF/Al3Fe5O12 hybrid material to a commercial level, in this work we adopted a simple strategy of electrospinning, and various degrees of Al3Fe5O12 nanoparticles incorporations have been tested to manipulate the strength of the interaction between the two diverse materials. Systematic studies have been conducted to elucidate the arrangement of PVDF chains in the electroactive β-phase configuration. Furthermore, magnetic studies have been conducted in this work to validate the existence of magnetic ordering in the PVDF/Al3Fe5O12 hybrid material systems. A high magnetoelectric coupling coefficient (6.19 mV cm−1 Oe−1) has been noticed for the PVDF/Al3Fe5O12 hybrid material containing 16 wt % Al3Fe5O12 nanoparticles. The evolution of defects with the incorporation of Al3Fe5O12 nanoparticles has been further explored using positron annihilation spectroscopy, which revealed the presence of free volume defects in large concentrations which evolve into Al3Fe5O12 nanoparticles decorated cavities with increased filler loading. The multifunctional nature enables the fabricated PVDF/Al3Fe5O12 hybrids as promising materials for the development of smart devices.