The local structures of various Bronsted and Lewis acid sites in H-Beta zeolite were resolved with the combined (31)p MAS NMR, (31)p-Al-27 TRAPDOR NMR experiments and theoretical calculations at different levels. In addition, the interacting mechanisms of these acid sites with probe molecules such as trimethylphosphine (TMP) and trimethylphosphine oxide (TMPO) were clarified,which greatly aids the understanding of acid catalysis. Owing to the narrow chemical shift range and close Bronsted acid strengths, only an average resonance at -4.5 ppm was observed in TMP adsorbed H-Beta zeolite, consistent with the calculated data of acidities (Substitution energies and proton affinities), geometries, adsorption energies as well as (31)p chemical shifts. However, two types of Bronsted acids were distinguished by TMPO, and the HF/DZVP2 (MP2/DZVP2) chemical shifts were calculated at 68.1 (69.5) and 69.7-72.1 (71.7-74.9)ppm, respectively. Two types of Lewis acids were identified at -32.0 and -47.0 ppm with the latter exhibiting strong P-31-Al-27 TRAPDOR effects. With theoretical calculations, these two peaks were attributed to the extra-lattice oxo-AlOH2+ species and the three-fold coordinated lattice-Al, extra-framework Al(OH)(3), oxo-AlO+ species, respectively. The peak at -60.0 ppm was conventionally assigned to the TMP physisorption, but the calculations indicated that the EFAL monovalent Al(OH)(2)(+) species coordinating with two lattice-O atoms near the framework All atom can contribute to it as well. (C) 2009 Published by Elsevier B.V.