We present the structure and a multinuclear solid-state NMR study of a new cyclic aluminophosphinate, The crystallographic structure of [Al-2(HC6H5PO2)(2)(C4H9OH)(8)]Cl-4 (compound 1) was obtained at low temperature (a = 11.830(7) Angstrom, b = 14.216(6) Angstrom, c = 17.790(6) Angstrom, beta = 91.25(4)degrees, monoclinic, P21/c, Z = 2). C-13 IRCP (inversion recovery cross polarization) and NQS (non quaternary suppression) NMR experiments allowed the complete assignment of the quaternary carbon atom of the phenyl ring and the precise determination of the isotropic \(1)J(P-C)\ coupling constant. P-31 CP MAS dynamics was carefully studied by varying the contact time. Dipolar oscillations even at slow MAS were observed. Up to 11 kHz, these oscillations were more pronounced, and the P-H distance was easily extracted. Al-27 NMR quadrupolar parameters for 1 were obtained with very good accuracy, and unusual satellite transition splitting was observed. Furthermore, the isotropic lines of the inner and outer transitions were clearly observable, leading to the unambiguous determination of the quadrupolar parameters.