Graphene p-n junctions have important applications in the fields of optical interconnection and low–power integrated circuits. Most current research is based on the lateral p-n junction prepared by chemical doping and other methods. Here, we report a new type of pure graphene oxide (pGO) vertical p-n junctions which do not dope any other elements but only controls the oxygen content of GO. The I–V curve of the pGO vertical p–n junction demonstrates a remarkable rectification effect. In addition, the pGO vertical p–n junction shows stability of its rectification characteristic over long-term storage for six months when sealed and stored in a PE bag. Moreover, the pGO vertical p–n junctions have obvious photoelectric response and various rectification effects with different thicknesses and an oxygen content of GO, humidity, and temperature. Hall effect test results show that rGO is an n–type semiconductor; theoretical calculations and research show that GO is generally a p–type semiconductor with a bandgap, thereby forming a p–n junction. Our work provides a method for preparing undoped GO vertical p–n junctions with advantages such as simplicity, convenience, and large–scale industrial preparation. Our work demonstrates great potential for application in electronics and highly sensitive sensors.