Small-sized silver nanoparticles are incorporated into a thiol-functionalized stable Zr-based metal-organic framework (MOF). Thiol functionalization has been carried out using 2-mercapto benzoic acid (2-MBA) as the modulator, which promotes defect formation in the MOF structure. The incorporation of silver nanoparticles aided by the silver-sulfur interactions in this defective MOF gives rise to catalytic activity. Its catalytic efficiency in the highly atom-efficient A3 coupling reaction has been studied for a variety of substrates with impressive recyclability. The synergistic effect of the electron-rich silver core and electron-deficient surface of the thiol-bonded silver nanoparticle is key for this catalytic reaction.