Samples of beta-zeolite thermally treated at different temperatures and acid leached with diluted hydrochloric acid solution have been investigated by XRD, Al-27 MAS-NMR spectroscopy and FTIR spectroscopy. The results have been used to interpret the behaviour of the samples as catalysts for the acylation of 2-methoxy-naphthalene. It has been shown that the as prepared sample presents two types of extraframework species. These are identified as Al hydroxo-ions highly dispersed in the internal zeolite channels and Al oxide nanoparticles. Calcination causes dealumination of the framework and progressive conversion of the Al hydroxo-ions into Al oxide nanoparticles that reduce the zeolite channels practicability, modifying the shape selectivity effect. The Bronsted acid sites present in the sinusoidal channels (nu(OH)=3608 cm(-1)) can be distinguished from those located in the larger ones (nu(OH)=3620-3612 cm(-1)), due to the inability of the bulky probe molecule pivalonitrile to enter the former. However, internal terminal silanols (nu(OH)=3735 cm(-1)) also apparently display a significant Bronsted acidity, definitely higher than the acidity of those absorbing at 3747 cm(-1), thought to be located at the external crystal surface. The strongest Lewis acidity is displayed by the aluminum hydroxo-ions, while that of alumina nanoparticles is a little weaker. Acid-leached beta-zeolite also displays a medium strength Lewis acidity, likely due to framework Al cations. Thus a partial reinterpretation of the real structure of beta-zeolite and a partial reassignment of the bands due to the surface hydroxy groups are proposed