Abstract: | Self‐assembly of metal nanoclusters into 3D ordered superstructures and the exploration of their electrochemical properties are highly significant for fundamental research and practical application. In this study, atomically precise Ag6(NALC)5 nanoclusters are successfully synthesized and their structure is determined carefully. It is interesting that the prepared Ag6(NALC)5 nanoclusters can be self‐assembled into ultrafine nanowires, long ribbons, and finally 3D porous network in the mixed solution of water and ethanol, which can be attributed to the solvent polarity, static electricity interaction between ligands, and the possible Van der Waals attractions. Such assembly phenomenon lays a foundation for the future fabrication of silver clusters‐based nanodevices. In addition, the synthesized silver nanoclusters can be used for electrochemical sensing of glucose with high detection sensitivity, selectivity, and low limit of detection. This work is expected to be helpful for the synthesis of atomically precise metal nanoclusters and their applications in fabrication of nanodevices for chemical sensors. |