A core-shell structured composite material with a mesoporous aluminosilicate (MAS) shell and mesopore-containing SSZ-13 (meso-SSZ-13) core was first synthesized by combining controlled desilication with subsequent self-assembly. The corresponding catalyst was subsequently prepared by a copper ion-exchange method. This catalyst can simultaneously solve three major problems existing in the previous Cu-SSZ-13 catalyst for NOx emission control from diesel engine exhaust, i.e., low temperature activity, hydrothermal stability and propene poisoning resistance. In comparison with Cu-SSZ-13, the meso-Cu-SSZ-13@mesoporous aluminosilicate (meso-Cu-SSZ-13@MAS) catalyst showed higher SCR activity across the entire temperature range. This increase was observed due to increasing the amount of active Cu species (isolated Cu2+ ions) and fewer pore diffusion limitations. The MAS shell with a “concrete with crushed stone”-like mesostructure could prevent the dealumination of meso-SSZ-13 core effectively, and therefore enhanced the hydrothermal stability of the meso-Cu-SSZ-13@MAS catalyst. Additionally, meso-Cu-SSZ-13@MAS exhibited higher hydrocarbon poisoning resistance because its external surface has fewer active sites for propene oxidation reaction.