In this study, poly(ε-caprolactone) based fibrous mats incorporating graphene oxide-silver hybrid nanocomposite as a nanofiller were successfully prepared by electrospinning method for potential biomedical applications. First, graphene oxide-silver nanoparticles (GO-AgNPs) were synthesized and the obtained GO-AgNPs nanohybrid was characterized by different analytical techniques. It was observed that the obtained AgNPs, with an average size of 5 ± 0.5 nm and spherical shape, were uniformly anchored on the surface of GO. Then, the synthesized GO-AgNPs were added into PCL to improve its tensile and bactericidal performances. The structural, morphological, mechanical and wettability properties of PCL-based fibrous mats as well as the release of silver ion release from PCL matrix were examined. Based on the results, we found that the addition of GO to the PCL-3.0%Ag nanofibers resulted in increased hydrophilicity, tensile strength and resistance to elastic deformation, and the PCL-GO-3.0%Ag sample also had a significantly higher release of silver ions. Besides, PCL-GO–3.0%Ag mats showed good antibacterial activity against Staphylococcus aureus and Escherichia coli compared to the PCL, PCL-GO and PCL-Ag nanofibrous mats. In summary, this study showed that PCL-GO–3.0%Ag nanofibrous mats could be a promising biomaterial for potential antibacterial applications.