Catalyst-free p-n homojunction ZnO nanowire (NW) arrays in which the phosphorus (P) and zinc (Zn) served as p- and n-type dopants, respectively, have been synthesized for the first time by a controlled in situ doping process for fabricating efficient ultraviolet light-emitting devices. The doping transition region defined as the width for P atoms gradually occupying Zn sites along the growth direction can be narrowed down to sub-50 nm. The cathodoluminescence emission peak at 340 nm emitted from n-type ZnO:Zn NW arrays is likely due to the Burstein-Moss effect in the high electron carrier concentration regime. Further, the electroluminescence spectra from the p-n ZnO NW arrays distinctively exhibit the short-wavelength emission at 342 nm and the blue shift from 342 to 325 nm is observed as the operating voltage further increasing. The ZnO NW p-n homojunctions comprising p-type segment with high electron concentration are promising building blocks for short-wavelength lighting device and photoelectronics.