Piezoelectric ceramic nanomaterials have recently attracted attention in the biomedical field thanks to their interesting electrical properties in response to mechanical stimulation (and vice versa) combined with a good biocompatibility and the ability to promote the regeneration of electrically sensitive tissues. In tissue engineering approaches, in order to obtain smart scaffolds these materials must be combined with other biomaterials for processing through conventional as well as non-conventional technologies. In this work, a novel composite electrospun membrane was produced by combining extracellular matrix-like gelatin nanofibers with barium titanate nanoparticles (BTNPs). The electrospinning process was optimized to achieve a high BTNP load, reducing the formation of aggregates which could alter the morphology and stability of the membrane. A complete morphological, mechanical and chemical-physical characterization of the composite membranes was performed, confirming the integration of the BTNPs into the polymer fibers. Furthermore, the biocompatibility of the developed membranes was assessed using a sarcoma osteogenic cell line (SaOS-2).