A series of porous pillared-zirconium phosphates functionalized with methyl, ethyl, propyl and phenyl groups were prepared and characterized by SEM, Si-29 MAS NMR, TG and N-2 adsorption. Their total surface acidity and accessible one were measured by potentiometric titration of n-butylamine and liquid phase 2,6-di-tert-butyl-pyridine adsorption, respectively. The catalytic behaviors of these hybrid materials for alkylation of hydroquinone and esterification of lauric acid were compared. Not the total acid sites but the accessible ones play a crucial role in both reactions of alkylation and esterification. The accession for acid sites can be enhanced by the introduction of alkyl/aryl groups, due to the improved hydrophobicity of the surface. (C) 2013 Elsevier B.V. All rights reserved.