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Pure and Mn-doped barium titanate nanofibers were synthesized by the electrospinning method. The morphology, microstructure and crystal structure of as-spun and annealed composite nanofibers were characterized by scanning electron microscopy and transmission electron microscopy. After annealing at 850°C, we obtain nanofibers a few μm long, formed by nanoparticles of irregular shape with sizes around 100 nm. X-ray diffraction and Raman spectroscopy show that a partial phase transition from tetragonal to hexagonal takes place for BaTi 0.90 Mn 0.10 O 3 . Vibrational phonon modes were calculated for BaTiO 3 within the density functional theory (DFT) framework. Ferroelectricity has been probed on pure and Mn-doped BaTiO 3 nanofibers, by means of piezoresponse force microscopy in an atomic force microscope, confirming the polar domain switching behavior of the fibers. The measured piezoelectric coefficient d 33 were 31 and 22 pm/V for BaTiO 3 and BaTi 0.90 Mn 0.10 O 3 . Magnetic properties of the samples were probed in a superconducting quantum interference device. Diamagnetic and paramagnetic behaviors were found in pure and Mn-doped samples, respectively. K E Y W O R D S atomic force microscopy, barium titanate, electrospinning, ferroelectricity/ferroelectric materials, perovskites