Display omitted ► BaTiO3 nanofibers were fabricated by a facile electrospinning method. ► The BaTiO3 nanofibers calcined at temperatures below 650°C are amorphous. ► Intense visible photoluminescence was detected in amorphous BaTiO3 nanofibers. ► PL performance exhibited a strong dependence on the calcination temperature. ► Highly disordered structure may be responsible for the intense photoluminescence. Broad visible emission at the wavelength range of 400–800nm was obtained at room temperature in amorphous barium titanate (BaTiO3) nanofibers, which were prepared by electrospinning and calcined at low temperatures. Structure and morphology of the BaTiO3 nanofibers were investigated by X-ray diffraction (XRD), transmission electron microscope (TEM), thermo-analysis and Raman spectroscopy. XRD data shows that the BaTiO3 nanofibers calcined at temperatures below 650°C are amorphous, in which intense photoluminescence (PL) emission bands at 600nm have been detected. More importantly, PL performance of the BaTiO3 nanofibers exhibited a strong dependence on the calcination temperature. Observable emission was only found in the low-temperature treated fibers. Mechanism of the observed photoluminescence has been discussed. The achievements shown herein may be help to find new light-emitting materials.