The electrospinning technique has been successfully employed for the fabrication of porous BaMnO3 nanofibers, followed by different thermal treatment. The samples were studied by X-ray diffraction (XRD), scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDX), Fourier transform infrared (FT-IR) spectroscopy, and diffuse reflectance spectroscopy (DRS). The XRD pattern shows that the organics were completely removed in sample calcined at 800 degrees C and the hexagonal BaMnO3 nanofibers were obtained. The microstructural parameters such as crystallite size and lattice strain contributions to line broadening were estimated using Williamson-Hall (W-H) analysis. The morphology and average diameters of the prepared nanofibers were estimated from the SEM images. The SEM images of the calcined samples show porous structure. The optical properties were studied using UV-Vis diffuse reflectance spectroscopy (DRS) and photoluminescence (PL) spectra. The optical bandgap of the calcined nanofibers decreased with an increase in calcination temperature from 700 to 800 degrees C. The PL spectrum shows that BaMnO3 nanofibers increased the radiative centers. We thus conclude that BaMnO3 nanofiber shows luminescent property.