We show in this communication that large-scale necklace-like single-crystalline tetragonal perovskite PbTiO3 nanowires can be obtained via a simple electrospinning method. The morphology and the crystal structure are investigated by SEM, XRD, and HRTEM. The length of the necklace-like PbTiO3 nanowires is from tens to several tens of micrometers, the wider the diameter of it is between 100 and 200 nm and the thinner the part is between 20 and 50 nm. The necklace-like PbTiO3 nanowires exhibit high surface photovoltage under the action of external electric field, which is probably applicable in displaying photoelectric devices of heterojunction structure.