Microwave (MW)-assisted heating, due to its unique properties has been used for synthesis of metal, oxide, zeolite, and metal-organic framework (MOF), and even to carry out organic reactions. However, less attention has been paid to integration of two or more functional components into advanced materials by MW-assisted strategy. We report herein for the first time for controllable integration of silver nanoparticles (NPs) and IRMOF-3 as a core-shell Ag@IRMOF-3 nanostructures into highly efficient catalysts by a facile one-pot MW irradiation method. Impressively, the uniform core-shell Ag@IRMOF-3 nanostructures can be fabricated as short as 5 min and are highly active for three-component coupling reaction of amine, aldehyde and acetylene (A(3)-coupling) by MW-assisted heating strategy. Specifically, the Ag@IRMOF-3 with average size of Ag NPs of 5.2 nm and IRMOF-3 of 91.5 nm exhibited the highest turnover numbers and turnover frequencies of 3052 and 149,00411(-1) reported up to date, respectively, for the PO-coupling reaction. Thanks to the MOF shell coating, the Ag@IRMOF-3 can be recycled at least for 8 runs without losing any activity; furthermore, the size-selective catalysis was also successfully achieved due to the size selective for propargylamines with different sizes. (C) 2017 Elsevier Inc. All rights reserved.