In present work, a multifunctional piezoelectric/photoluminescence effect, which originated from the combination of the piezoelectric properties and the photoluminescence effect, was realized in one-dimensional Er3+ doped lead-free BaTiO3 nanofibers prepared by a sol-gel based electrospinning method. The X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM) were utilized to characterize the morphologies and phase structures. The effect of the host crystallization and rare-earth concentration on the structure and photoluminescence properties was studied. In addition, temperature-dependent PL spectrum exhibited a piezoelectric/photoluminescence coupling effect, characterized by the enhanced photoluminescence intensity around the ferroelectric-paraelectric phase transition temperature of BaTiO3. (C) 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.