Experimental adsorption isotherms were used to evaluate the specific surface area and the surface fractal dimensions of acid-activated bentonite samples modified with a heteropoly acid (HPW). The aim of the investigations was to search for correlations between the specific surface area and the geometric heterogeneity, as characterized by the surface fractal dimension and the content of added acid. In addition, mercury intrusion was employed to evaluate the porous microstructures of these materials. The results from the Frankel-Halsey-Hill method showed that, in the p/p sub(0) region from 0.75 to 0.96, surface fractal dimension increased with increasing content of heteropoly acid. The results from mercury intrusion porosimetry (MIP) data showed the generation of mesoporous structures with important topographical modifications, indicating an increase in the roughness (fractal geometry) of the surface of the solids as a consequence of the modification with the heteropoly acid. By comparison, MIP is preferable for the characterization because of its wide effective probing range.