Preparing electrospun fibers by applying a potential difference between a polymeric solution and a contacting substrate is increasingly attracting attention in tissue engineering applications. Among the numerous polymers, polycaprolactone (PCL) bioscaffold has been widely investigated due to its biocompatibility and biodegradability. Bioactive powder can be added to further improve its performance. In the present study, bioactive glass powder modified by adding 0-6 wt.% antibacterial zinc element (coded as ZBG) was prepared through the sol-gel process. Furthermore, PCL bioscaffolds with various ZBG additions were prepared using the electrospinning technique. The zinc-doped bioactive glass powder and electrospun PCL/ZBG bioscaffolds were evaluated using scanning electron microscopy, X-ray diffraction and Fourier-transform infrared spectroscopy to determine their structural properties. Additionally, in vitro bioactivity, biocompatibility and antibacterial performance were investigated. Experimental results showed that sol-gelled ZBG powder possessed superior bioactivity and 0.8 g ZBG was the optimal addition to prepare PCL/ZBG bioscaffolds with. All the electrospun PCL/ZBG bioscaffolds were biocompatible and their antibacterial performance against two strains (SA133 and Newman) improved with increasing zinc concentration. Electrospun PCL/ZBG bioscaffolds exhibited excellent bioactivity and have great potential for biomedical application.