In this study, the bioactivity and cytocompatibility of electrospun polyamide 6 (PA6)/hydroxyapatite (HA) coating on zirconia-toughened alumina (ZTA) were investigated. Adjusting the PA6/HA ratio to 1.15 (w/w) had a significant role in achieving an appropriate fibrous coating with an average diameter of 120 ± 10 nm and surface porosity of 64.3%. The surface of bare and coated samples was hydrophilic, which promoted bone regeneration. The adhesion test of the PA6/HA mat demonstrated that a cohesive coating was formed on the ZTA via electrospinning. The in vitro bioactivity test of the PA6/HA coating in simulated body fluid (SBF) corroborated the formation of a nanostructured bonelike apatite phase. Cytocompatibility of the samples was evaluated through in vitro osteosarcoma-like cell (MG63) culture assays. The cytotoxicity study showed that the electrospun PA6/HA coating significantly improved cell attachment and spreading. The development of such bioactive, biomedical coatings opens new avenues for bone tissue engineering applications.