Si-Al oxide based materials are catalyst materials which can be used in different processes due to their advantages of diversified pore structures, adjustable pore sizes, large specific surface areas, being easily loaded with active metals and grafted with organic functional groups, all of which could improve the reaction activity and selectivity. Importantly, ordered mesoporous materials with large pore sizes exhibit preferable characteristics in catalytic reactions, good distribution of the active sites, and efficient capability in the mass transfer and diffusion of reactants, intermediates and products. In this paper, different expanding agents that are usually used to synthesize ordered mesoporous materials were summarized in detail, and the related influences on the channel structure, physical and chemical properties were reviewed. Furthermore, chemical and physical methods were reviewed, including acid or base post-processing methods which are usually used in the modification of microporous materials, and the addition of polar or nonpolar expanding agents into the original reaction systems which are often adopted in the synthesis of mesoporous materials. Moreover, research progress in the mechanisms of the expanding agents and their effects on the material properties were also summarized, and then the future trends for using expanding agents in the synthesis of ordered mesoporous materials were discussed, thus providing important information for the structural design and optimization of novel materials and catalysts.