A facile and effective growing strategy of graphite-like carbon nitride quantum dots (CNQDs) modified on ZnO nanowire array composite electrodes has been successfully designed and prepared for the first time. The remarkable quantum enhanced properties were carefully studied by means of scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscope (XPS), UV-vis diffuse reflectance, PEC performance, and photocatalytic hydrogen production, and the results were in good agreement. Fivefold enhanced photoelectrochemical performances of this novel hierarchical hetero-array prepared in this paper compared with pure ZnO nanowire arrays were obtained under UV-light. The effect was attributed to the remarkable charge separation between CNQDs and ZnO nanowire arrays. Additional investigations revealed that the particular structure of CNQDs/ZnO composites contributed to the separation of a photon-generation carrier and an enhanced photoelectric current. Moreover, the absorption edge of CNQD-modified ZnO nanowire arrays was slightly broadened, and the diameter was reduced as well. The photoelectrochemistry hydrogen evolution splitting water using simulated solar irradiation exhibited the foreground of a possible application of a mechanism of photoelectrochemistry hydrogen evolution over CNQDs/ZnO composite electrodes.