A new 3D organo-silver(I) crystalline complex of [(MPC) 4 (CF 3 COO) 8 Ag 10 ] n (MPC = 4-methyl-7-propargyloxy coumarin) (JMSU-Ag 10 ) has been successfully synthesized. The crystal structure analysis shows that the 10-core silver(I) cluster (Ag 10 ) can be considered as the subunit of JMSU-Ag 10 with different Ag⋯Ag argentophilic interactions. By the protection of organic ligands and Ag⋯Ag interactions, the Ag 10 subunits further compose a chain structure, and then the trifluoroacetate or the MPC ligands bridge the 1D silver(I) chains along different directions to form the 3D framework. Furthermore, JMSU-Ag 10 can be used to detect the hydrazine due to that the Ag + ions can be reduced to Ag 0 species with strong UV-vis absorption. Interestingly, the reduced JMSU-Ag 10 by hydrazine can be further used to catalyze the reduction of 4-nitrophenol to form 4-aminophenol. This work provides a new strategy for the design, synthesis, and the cyclic utilization of functional organo-silver(I) crystalline materials.