Electrospinning as a versatile technique producing nanofibers was employed to study the influence of the processing parameters and chemical and physical parameters of solutions on poly(vinylidene fluoride) (PVDF) fibers’ morphology, crystallinity, phase composition and dielectric and piezoelectric characteristics. PVDF fibrous layers with nano- and micro-sized fiber diameters were prepared by a controlled and reliable electrospinning process. The fibers with diameters from 276 nm to 1392 nm were spun at a voltage of 25 kV–50 kV from the pure PVDF solutions or in the presence of a surfactant—Hexadecyltrimethylammonium bromide (CTAB). Although the presence of the CTAB decreased the fibers’ diameter and increased the electroactive phase content, the piezoelectric performance of the PVDF material was evidently deteriorated. The maximum piezoelectric activity was achieved in the fibrous PVDF material without the use of the surfactant, when a piezoelectric charge of 33 pC N⁻¹ was measured in the transversal direction on a mean fiber diameter of 649 nm. In this direction, the material showed a higher piezoelectric activity than in the longitudinal direction.

Nanofibers are well known as a beneficial type of structure for tissue engineering. As a result of the high acquisition cost of the natural polymers and their environmentally problematic treatment (toxic dissolution agents), artificial polymers seem to be the better choice for medical use. In the present study, polycaprolactone nano-sized fibrous structures were prepared by the electrospinning method. The impact of material morphology (random or parallelly oriented fibers versus continuous layer) and the presence of a fraction of hydroxyapatite nanoparticles on cell proliferation was tested. In addition, the effect of improving the material wettability by a low temperature argon discharge plasma treatment was evaluated, too. We have shown that both hydroxyapatite particles as well as plasma surface treatment are beneficial for the cell proliferation. The significant impact of both influences was evident during the first 48 h of the test: the hydroxyapatite particles in polycaprolactone fibers accelerated the proliferation by 10% compared to the control, and the plasma-treated ones enhanced proliferation by 30%.