An unprecedented class of benzoyldiazenido-functionalized polyoxometalates, [Bu 4 N] 3 [Mo 6 O 18 (=N=NCOAr)] (Ar= Ph, 1; Ph-o-Cl, 2; Ph-m-Cl, 3; Ph-p-Cl, 4; Ph-o,p-Cl 2 , 5; Ph-p-Br, 6;Ph-m-NO 2 , 7; Ph-p-NO 2 , 8; Ph-p-OMe, 9), are prepared through the reactions of α-octamolybdate and the corresponding hydrazides in dry acetonitrile under reflux with dicyclohexylcarbodiimide (DCC) as a dehydrating agent. Single-crystal X-ray diffraction structural analysis reveals that their anions demonstrate the typical structural features of monofunctionalized hexamolybdates with different organic substituents. 1 H NMR [a]