Reaction of multidentate 5-(4-imidazol-1-yl-phenyl)-2H-tetrazole (L) ligand with Ag(I) ions in the existence of H(3)PW(1)2O(4)0 as anionic template under hydrothermal conditions results in tridecanuclear silver cluster-polyoxometalates hybrid: {Ag13L12}{PW12O40}(4).30H(2)O (1). X-ray single crystal diffraction analysis indicates that the main structural feature of 1 is a nanosized molecular windmill-shaped polynuclear Ag cluster with intriguing {M@M-12}-type cuboctahedral topology. The as-synthesized compound exhibits effective photocatalytic activity in the photodegradation of Rhodamine-B (RhB) and antibacterial activity against Escherichia coli, respectively.