Micro/meso/macroporous (hierarchical) zeolites show remarkable catalytic performance for reactions involving bulky reactants. However, quantitative assessment of the microstructural characteristics contributing to the observed performance remains elusive. Here, structure-activity relationships are established for a set of micro/mesoporous self-pillared pentasil (SPP) zeolites using two parallel liquid-phase reactions (benzyl alcohol alkylation and self-etherification) based on analysis of mass transport and reaction kinetics. A reaction-diffusion mathematical model is developed that quantitatively assigns the catalytic contributions of the external surface and micropores of SPP zeolites for these reactions. In addition, the effect of the zeolite external surface structure on the corresponding catalytic activity is quantitatively assessed by comparing SPP zeolites (with MFI structure) with MCM-22 (with MWW structure). This work demonstrates that reaction-diffusion modeling allows quantitative description of the catalytic performance of hierarchical zeolites and provides a model reaction to assess nm-sized characteristic diffusion lengths in MFI. (c) 2018 American Institute of Chemical Engineers