Two polyanion clusters [Mo36O108(NO)4(H2O)16]12 ?/sup> (1) and [Mo36O112(H2O)16Cu0.5(H2O)2]7 ?/sup> (2) were obtained through ¡®one-pot?reaction at ambient temperature and pressure. Both of 1 and 2 consist of {Mo36} anionic clusters. Interestingly, compound 2 represents a case that the transitional metal copper is anchored into the framework of a giant {Mo36} isopolyanion.