High activity boron nitride/titanium dioxide (BN/TiO2) composite nanofiber photocatalysts were synthesized for the first time via the electrospinning technique. The as-spun nanofibers with a controlled ratio of boron nitride nanosheets (BN) were calcined under air at 500 °C for 4 hours. Their morphological, structural and optical properties were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), BET surface area, Fourier-transform infrared (FTIR), Raman spectroscopy, UV-Visible spectrophotometry and room temperature photoluminescence (PL). The effect of loading different BN sheet amounts on the photocatalytic degradation of methyl orange (MO) was investigated. The results indicated that the presence of BN sheets improved the separation of the photo-induced electron–hole pairs in TiO2 and increased the band gap energy and the specific surface area compared to pure TiO2 nanofibers. BN/TiO2 (10 wt%) composite nanofiber photocatalytic activity is enhanced to 99% compared to 60% and 65% for P25 and TiO2 nanofibers, respectively. Thus, the BN/TiO2 composites significantly increase the UV light photo-response and improve the separation of photo-induced electron–hole pairs of TiO2