An electrospinning-calcination strategy was established to fabricate Y2O3 nanofibers doped with rare earth ions (Tb, Sm and Dy) using electrospun PVA/RE(NO3)(x)/Y(NO3)(3) composite nanofibers as precursors (x=3.4). The prepared nanofibers were characterized by XRD, FESEM, EDS, (HR)TEM and PL analyses. Based on the experimental results, a solid-solid growth mechanism (SS) was proposed to describe the formation of inorganic crystalline fibers from organic/inorganic composite nanofibers by calcination. It was determined that carbonaceous nanoparticles that were formed in the process of pre-carbonization adsorbed Y2O3:RE nanoparticles to grow Y2O3:RE crystal, and the resultant nanofibers exhibited a typical crystalline domain with grain boundary. The obtained Y2O3:RE nanofibers possessed excellent luminescent characteristics and could be used as an appreciable luminescent material. (C) 2011 Elsevier B.V. All rights reserved.