Boron doped and undoped Bi2O3-Y2O3 nanofibers were synthesized by the electrospinning method. The nanofibers were then calcined to obtain nanocrystalline ceramics. The synthesized nanofibers and nanocrystalline ceramics were characterized using XRD, FT-IR, SEM and XPS. According to the XRD results the undoped Bi2O3-Y2O3 nanocrystalline ceramic has a face-centered cubic structure. The XPS results show that nanocrystalline ceramics were pure Bi2O3, and there were no peaks related to either bivalent or tetravalent or pentavalent states in Bi2O3. The XPS results also show that the crystallinity of the boron doped nanocrystalline ceramic was decreased because of the network former property of the boron. The average fiber diameters for electrospun boron doped and undoped PVA/Bi-Y acetate nanofibers were calculated as 179 nm and 96 nm, respectively. The SEM micrographs of the nanocrystalline ceramics show that the undoped Bi2O3-Y2O3 ceramic has needle-like crystalline structure. However, the crystallinity of the boron doped Bi2O3-Y2O3 ceramic decreased because of boron doping. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.