The Mo modiifed Ni/Al2O3 catalysts were prepared and sulifded at different temperatures, and their catalytic acti-vity for thioetheriifcation of mercaptans and oleifns (or dienes), hydrogenation of dienes and oleifns in the thioetheriifcation process using lfuidized catalytic cracking (FCC) naphtha as the feedstock was investigated. In order to disclose the correla-tion between the physicochemical characteristics of catalysts and their catalytic activity, the surface structures and properties of the catalysts sulifded at different temperatures were characterized by the high resolution transmission electronic micro-scopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and H2-temperature programmed reduction (H2-TPR) technique. The results showed that an increase of sulfurization temperature not only could promote the sulfurization degree of active metals on the catalysts, but also could adjust the micro-morphology of active species. These changes could improve the catalytic performance of thioetheriifcation, and hydrogenation of dienes and oleifns. However, an excess sulfurization tem-perature was more easily to upgrade the ability of the catalyst for hydrogenation of oleifns, which could lead to a decrease of the octane number of the product. It was also showed that a moderate sulfurization temperature not only could improve the catalytic performance of thioetheriifcation and hydrogenation of dienes but also could control hydrogenation of oleifns.