Designing and fabricating catalysts with highly dispersed metal nanoclusters (NCs) is very crucial for achieving high activity and selectivity. In this work, all-alkynyl-protected [Ag-74(C CPh)(44)](NO3)(2) cluster (Ag duster) with a well-defined structure was firstly intercalated in alpha-zirconium phosphate (alpha-ZrP) through ion-exchange. Then the atomically precise Ag cluster can be immobilized robustly in the support by a sequential process of carbonization, calcination and reduction. The supported Ag duster showed the relatively high catalytic activity (TOP = 222.9-445.8 h(-1)) and excellent recyclability for hydrogenation of a variety of nitroaromatics, as well as the compounds with carbon-carbon double bonds even if the loading of Ag was as low as 0.72 wt.%. Zirconium pyrophosphate acts as not only a stabilizer of Ag duster through a spatial confinement, but also an adsorption site for nitroaromatics. The residual carbon arisen from thermal decomposition of all-alkynyl ligand coordinating on Ag cluster exerted an important role in protecting Ag duster from sintering. As a result, the intercalation of Ag cluster in the interlayer region is a promising strategy for extending their potential applications in catalysis.