The influence of postsynthesis treatment such as calcination and acid treatment of zeolite HBEA has been studied in the acylation of 2-methoxynaphthalene with acetic anhydride. The contribution of the inner and outer surface of zeolite HBEA is examined by conversion and product selectivity to a bulky product, which can be formed only on the outer surface of HBEA, and to a linear product, which can be formed on the inner and outer surfaces. Calcination under high heating rate enhances the catalytic activity of the inner surface due to the formation of extraframework alumina species in the micropores. FTIR-adsorption experiments of the bulky probe molecule 2,4,6-tri-tert-butylpyridine, which does not fit into the micropores, revealed that these alumina species are located preferentially in the micropores of HBEA. Acid treatment increases the catalytic activity of the outer surface due to the extraction of catalytically active extraframework alumina species out of the micropores and due to the formation of silanol groups, respectively.