Fe- and Mn-promoted ZrO2-SO4 (ZS) powders were prepared both by a single step sol-gel reaction and by impregnation of the zirconia hydrous precursor. The samples were calcined at 890 K and characterized for the structural (XRD) and morphological features (BET method). Surface functionalities were investigated by XPS, H-1 MAS NMR and FTIR analyses. The liquid medium catalytic activity was tested with respect to both the esterification of benzoic acid to methylbenzoate and the benzylation of toluene. The acidity features appeared not to be significantly different among the various samples while all surface characterizations showed a lower affinity to retain water by the metal-promoted samples with respect to ZS, the more so in the case of iron-containing samples. The presence of Mn reduced the surface area and depressed the catalytic activity. Iron-doped catalysts appeared, instead, to be more efficient than ZS especially for the benzylation of toluene. (c) 2009 Elsevier B.V. All rights reserved.