La-doped p-type ZnO nanofibers were successfully synthesized by electrospinning, followed by calcination. The microstructure and morphology of the La-doped ZnO nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The field effect curve of individual nanofibers confirms that the resulting La-doped ZnO fibers are p-type semiconductors. The doping mechanism is discussed. Furthermore, crossed p–n homojunction nanofibers were also prepared based on electrospun La-doped p-type ZnO and n-type pure ZnO fibers. The current–voltage curve shows the typical rectifying characteristic of a p–n homojunction device. The turn-on voltage appears at about 2.5 V under the forward bias and the reverse current is impassable.