Three novel WWZr-substituted polyoxotungstate aggregates [H2N(CH3)(2)](7)NaH2[Zr2Sb2O3(A-alpha-PW9O34)(2)]center dot 16H(2)O (1), [H2N(CH3)(2)](6)H-12[ZrSb4(OH)-O-2(A-alpha-PW8O32)(A-alpha-PW9O34)]2 center dot 33H(2)O (2), and [H2N(CH3)(2)](4)Na11.5H4.5[Zr4W8Sb4P5O49(OH)(5)(B-alpha-SbW9O33)(2)]center dot 53H(2)O (3) have been made in hydrothermal reactions of the [B-alpha-SbW9O33](9-) precursor with Zr4+ cations and PO43- anions in the presence of dimethylamine hydrochloride and sodium acetate buffer (pH = 4.8) and structurally characterized. Different pH values induce structural transformation from tungstoantimonate (TA) to tungstophosphate (TP). 1 is a di-Zr-substituted sandwich-type TP, the tetranuclear heterometallic [Zr2Sb2O3](8+) entity sandwiched by two [A-alpha-PW9O34](9-) moieties. 2 is a double sandwich-type structure, which can be perceived as two equivalent sandwiched [Sb-3(PW8O32)(PW9O34)](11-) further sandwiching one [Sb2Zr2(OH)(2)O-4](4+) core to form a novel large-size sandwich-type architecture. Different from 1 and 2, 3 is a tetra-Zr-substituted sandwiched configuration, in which two [B-alpha-SbW9O33](9-) fragments sandwich a unique 21-core SbPWZr oxo cluster ({Zr4W8Sb4P5}). Furthermore, the catalytic oxidation of aromatic thioethers by 3 as the heterogeneous catalyst has been investigated, showing high conversion and remarkable selectivity as well as excellent recyclability.