Core-shell-structured SBA-15@MgAl2O4 (abbreviated as S@MA) was prepared by homogeneous precipitation through sol-gel method. The effects on the properties of S@MA as a supporting material have been investigated in comparison with MA and SBA-15. The results showed that the pore structure was changed, the acid sites were introduced, and the surface properties were improved by the construction of the core-shell-structured S@MA. Then, these materials were used as the carrier for the catalysts by impregnation method. Moreover, in PtSnNa/S@MA, these modifications not only decreased the size of surface Pt ensembles, but also changed the interfacial character between metal and support. In addition, compared to PtSnNa/MA, the capacity of the catalyst which supports on S@MA to accommodate coke was improved and the carbon deposit on PtSnNa/S@MA was migrated from the active metal to the carrier. These intriguing results are attributed to larger surface area and the appearance of the acid sites in S@MA.