The aim of this study was to produce advanced nanofiber mats by adding boron nitride to poly (-caprolactone) polymer using an electrospinning method and to characterize the resultant structures. Pure poly (-caprolactone) nanofiber mats and boron nitride-doped nanofiber mats prepared at different concentrations were compared. The morphological structures of the nanofiber mats were examined under a scanning electron microscope, spectroscopic analyses were conducted using Fourier transform infrared spectroscopy, and thermal stability was analyzed using a thermogravimetric analysis method. Successful electrospinning of boron nitride-doped nanofibers at lower voltages was achieved. The thermogravimetric analysis test found that the thermal stability of boron nitride-doped nanofiber mats is higher than that of pure nanofibers, which suggests that the produced composite material could be preferable in applications involving insulation and high temperature. On the other hand, the Fourier transform infrared spectroscopy results indicated that no chemical reaction occurred between boron nitride and the poly (-caprolactone) nanofibers.