An environmentally friendly, low-cost, and large-scale method is developed for fabrication of Cl-doped ZnO nanowire arrays (NWAs) on 3D graphene foam (Cl-ZnO NWAs/GF), and investigates its applications as a highly efficient field emitter and photocatalyst. The introduction of Cl-dopant in ZnO increases free electrons in the conduction band of ZnO and also leads to the rough surface of ZnO NWAs, which greatly improves the field emission properties of the Cl-ZnO NWAs/GF. The Cl-ZnO NWAs/GF demonstrates a low turn-on field (≈1.6 V μm(-1)), a high field enhancement factor (≈12844), and excellent field emission stability. Also, the Cl-ZnO NWAs/GF shows high photocatalytic efficiency under UV irradiation, enabling photodegradation of organic dyes such as RhB within ≈75 min, with excellent recyclability. The excellent photocatalytic performance of the Cl-ZnO NWAs/GF originates from the highly efficient charge separation efficiency at the heterointerface of Cl-ZnO and GF, as well as improved electron transport efficiency due to the doping of Cl. These results open up new possibilities of using Cl-ZnO and graphene-based hybrid nanostructures for various functional devices.