In this paper, ZnO@MoS2 core-shell heterojunction arrays were successfully prepared by the two-step hydrothermal method, and the growth mechanism was systematically studied. We found that the growth process of molybdenum disulfide (MoS2) was sensitively dependent on the reaction temperature and time. Through an X-ray diffractometry (XRD) component test, we determined that we prepared a 2H phase MoS2 with a direct bandgap semiconductor of 1.2 eV. Then, the photoelectric properties of the samples were studied on the electrochemical workstation. The results show that the ZnO@MoS2 heterojunction acts as a photoanode, and the photocurrent reaches 2.566 mA under the conditions of 1000 W/m2 sunshine and 0.6 V bias. The i-t curve also illustrates the perfect cycle stability. Under the condition of illumination and external bias, the electrons flow to the conduction band of MoS2 and flow out through the external electrode of MoS2. The holes migrate from the MoS2 to the zinc oxide (ZnO) valence band. It is transferred to the external circuit through the glass with fluorine-doped tin oxide (FTO) together with the holes on the ZnO valence band. The ZnO@MoS2 nanocomposite heterostructure provides a reference for the development of ultra-high-speed photoelectric switching devices, photodetector(PD) devices, and photoelectrocatalytic technologies.