The desulfurization activity and selective hydrogenation of Cu/-ZnO adsorbents on the different polarity ratios of ZnO as supports was investigated in reactive adsorption desulfurization. The ZnO particles were synthesized by the hydrothermal process, and CuO/ZnO adsorbents were synthesized by incipient impregnation method. The structure and morphology of the ZnO and CuO/ZnO were characterized by X-ray diffraction (XRD), N-2, adsorption desorption, X-ray photoelectron spectra (XPS), scanning electron microscope/selected area electron diffraction (SEM/SAED), transmission electron microscopy (TEM), and temperature-programmed reduction (TPR). The surface area and polarity ratio of ZnO supports were controlled by the calcination temperature and concentration of P-123, respectively. More reactive activity sites were provided by the high surface area of ZnO supports, thus improving the desulfurization activity. The polarity ratio of ZnO may strongly influence the hydrogenation reactions of olefins. The selective hydrogenation increased with the value of polarity ratios.