Zn(OH) ₂ carbon composite microspheres were prepared by hydrothermal method using sucrose as template and then roasted to form the ZnO hollow microspheres. The effects of calcination rate on the morphology and pore structure of ZnO hollow microspheres were investigated. The structures of the hollow microspheres were characterized by XRD, TG, SEM and N ₂ adsorption. Then, the NiO/ZnO adsorbents with 5% Ni content were prepared by equal volume impregnation method. The results show that when the calcination rate is 3 ℃/min, the specific surface area and pore volume of hollow microspheres are as high as 37.21 m ²/g and 0.483 cm ³/g respectively; when the adsorption temperature is 350 ℃， the pressure is 1.2 MPa, the volume space velocity is 6 h ^-1 and the volume ratio of hydrogen to the simulated oil is 60, the desulfurization rate of the Ni/ ZnO adsorbent can reach as high as 96%， which has potential value in application.