The synthesis and crystal structure of a zirconocene derivative with α-Keggin mono-aluminum-substituted polyoxotungstate, [α-PW(11)Al(OH)O(39)ZrCp(2)](2)(6-) (Cp = C(5)H(5)(-)) (1), which was obtained by the reaction of α-Keggin mono-aluminum-substituted polyoxotungstate with a biscyclopentadienylzirconium(IV) complex, is described herein. Analytically pure, homogeneous, yellow crystals of the tetra-n-butylammonium salt of polyoxoanion 1, [(n-C(4)H(9))(4)N](6)[α-PW(11)Al(OH)O(39)ZrCp(2)](2) (TBA-1), were obtained from the ca. 1 : 1 reaction of [(n-C(4)H(9))(4)N](4)[α-PW(11){Al(OH(2))}O(39)] with Cp(2)Zr(OTf)(2)·THF (OTf = O(3)SCF(3)(-)) in acetonitrile solution under an argon atmosphere, followed by precipitation from water and crystallization from acetonitrile. TBA-1 was characterized based on X-ray structure analysis, elemental analysis, thermogravimetric/differential thermal analysis (TG/DTA), Fourier transform infrared (FTIR), and solution ((31)P, (27)Al, (19)F, (1)H, and (13)C) nuclear magnetic resonance (NMR) spectroscopy. Single-crystal X-ray structure analysis revealed that the two {PW(11)AlO(40)} units are bridged by two "bent sandwich" Cp(2)Zr(2+) fragments with C(2) symmetry. Each zirconium center was bound to a terminal oxygen atom of the aluminum and tungsten sites and an edge-sharing oxygen atom at the Al-O-W linkage. Further, the stability towards water was investigated by NMR ((31)P, (1)H, and (13)C) and FTIR spectroscopy. The η(5)-cyclopentadienylzirconium fragments were not eliminated from the surface of [α-PW(11){Al(OH(2))}O(39)](4-) even after 24 h exposure to 50 equiv. of water.