Volatile organic compounds (VOCs) are characterized by large emissions, a wide range of sources, and various types. Catalytic combustion, as one of the most efficient treatment technologies, has attracted much attention for its core technology, "the catalyst". However, even a trace amount of sulfur species containing VOCs can poison catalysts, resulting in a significant loss of its catalytic activity and lifetime. Therefore, it is crucial to improve the sulfur tolerance of the catalyst and study the sulfur poisoning process and deactivation mechanism during the catalytic degradation of VOCs. Understanding the sulfur poisoning process is key to develop catalysts with excellent catalytic performance for VOCs degradation. In this paper, the catalysts used for the catalytic degradation of VOCs mainly involve γ-Al_2O_3, Beta zeolite, and pillared clay as carriers, along with transition metal oxides andprecious metals as reaction active centers. Quantitative sulfur species are introduced into various fresh catalysts through in-situ (NH_4)_2SO_4 thermal decomposition, resulting in a series of catalysts with varying degrees of sulfur poisoning. The changes in the structure, redox, acidity, and other properties of the catalyst before and after sulfur poisoning are studied using the catalytic oxidation of toluene as a probe reaction. By combining this with the sulfur poisoning of the active sites, the structure-activity relationship between the catalyst structure and the catalytic performance for VOCs degradation is clarified, providing a deep understanding of the sulfur poisoning mechanism of the catalyst. By summarizing our recent research achievements in this paper, we hope to promote the development of high-performance catalysts for sulfur-containing VOCs catalytic combustion and provide a theoretical and technical basis for achieving the industrial application of catalysts under complex reaction systems.