1D superlattices with long‐ranged periodicity present extraordinary application properties due to their unique electronic structures. Here, the visible light driven synthesis of 1D single‐cluster chains constructed by polyoxometalate (POM) and Ag clusters is reported, where two types of clusters align alternatively along the nanowire. Low symmetrical POM clusters of [P2W17O61]10–, [P2W15O56]12–, and [EuW10O36]9– can be used as building blocks. The directly bonding cluster units result in interactive electronic structures of Ag and POM clusters, as well as the greatly promoted electron transfer during the redox reaction. The Ag–P2W17 nanowires perform significantly enhanced activities in both electrochemical sensing and catalytic gasoline desulfurization compared with individual building blocks, demonstrating the extraordinary application properties and promising potentials of cluster‐based heteroconstructions.

Polyoxometalates (POMs) are early transition metal oxide clusters with diverse structures and extensive functions. Due to the excellent redox property and stability, POM clusters can serve as ligands and supports...