This article is aimed at a basic physical characterization of electrospun PVDF/graphene oxide (GO) composite non-woven fibre mats. The morphological characterization of the prepared fabrics was performed via SEM investigations. Introduction of the GO during the electrospinning process caused significant changes in the crystalline structure of PVDF, and a transformation from alpha- to beta-crystalline phases was achieved. Addition of the GO particles into PVDF did not only improve the thermal stability of the polymer, but also acted as a reinforcing filler, giving rise to improved dynamic moduli and tensile strength. The dielectric properties were evaluated over a broad frequency range, and it was confirmed that the presence of small amounts of GO had little effect on the dielectric properties of the PVDF, since the GO has a dielectric character similar to that of the PVDF.