Heterogeneous catalysts with precise surface and interface structures are of great interest to decipher the structure-property relationships and maintain remarkable stability while achieving high activity. Here, we report the design and fabrication of the new sandwich composites ZIF-8@Au-25@ZIF-67[tkn] and ZIF-8@Au-25@ZIF-8[tkn] [tkn = thickness of shell] by coordination assisted self-assembly with well-defined structures and interfaces. The composites ZIF-8@Au-25@ZIF-67 efficiently catalyzed both 4-nitrophenol reduction and terminal alkyne carboxylation with CO2 under ambient conditions with remarkably improved activity and stability, compared to the simple components Au-25/ZIF-8 and Au-25@ZIF-8, highlighting the highly useful function of the ultrathin shell. In addition, the performances of these composite sandwich catalysts are conveniently regulated by the shell thickness. This concept and achievements should open a new avenue to the targeted design of well-defined nanocatalysts with enhanced activities and stabilities for challenging reactions.