A crystalline complex [Al8F12 {(CH3)(2)C(NH3)PO3}(12)] (1) was isolated from the supernatant of the hydrothermal reaction of gibbsite Al-(OH)(3) with 1-amino-1-methyl-ethylphosphonic acid ( AIPA) and the HF mineralizer. The single-crystal X-ray diffraction analysis revealed a highly symmetrical cubic Al8F12 core with aluminum atoms at the corners, bridging fluorides spanning all edges, and 12 bidentate bridging phosphonate ligands completing the octahedral coordination sphere of aluminum centers. The stability of the complex in solution was established by electrospray mass spectrometry and the high molecular symmetry (T-h) was reflected in the appearance of single resonances in the H-1, F-19, and P-31 NMR spectra.