Mo improved Ni/Al2O3 catalysts were prepared and characterized, which demonstrated good catalytic performance for thioetherification process of FCC gasoline. The physico-chemical properties of the Ni/Al2O3 catalysts with different amounts of Mo were characterized by physical techniques and were correlated with their catalytic performance. Experimental results showed that bimetal (Mo and Ni) based catalysts displayed superior catalytic performance than mono-metal (Ni) based catalysts. Addition of Mo to Ni catalysts could inhibit the formation of NiAl2O4 crystallites and facilitate the formation of active precursor NiMoO4, contributing to the formation of more active sites during the presulfidation process. The micro-morphology of active species was restructured and the needle-stacks of Ni-Mo-S were observed on the Mo improved catalysts. These structures and properties had important influence on the thioetherification. By optimizing the Mo/Ni atomic ratio, the catalysts with a Mo/Ni atomic ratio of 0.3 had suitable micro-morphologies and properties, exhibiting the best catalytic performance and selectivity for thioetherification.