In this work we use the hydroisomerization of n-hexane as a catalytic test reaction to investigate the shape selective properties of a series of zeolites (mordenite, V. ZSM-5, ZSM-12, TNU-9, SSZ-25, SSZ-26, SSZ-32, SSZ-33, SSZ-56, SSZ-57 and SSZ-75). The yield ratio of mono-branched isomers (2- and 3-methylpentane) to di-branched isomers (2,2- and 2,3-dimethylbutane) and the yield ratio of 2,3- to 2,2-dimethylbutane provide a useful tool for characterizing the effective pore sizes of zeolites. The high octane isomer 2,3-dimethylbutane (RON 101.0) can be selectively produced over 2,2-dimethylbutane (RON 91.8) by choosing zeolites (e.g., TNU-9 and SSZ-75) which have the appropriate pore sizes, demonstrating some new examples of the shape selectivities of zeolite catalysis. This catalytic test reaction is complementary to the vapor phase hydrocarbon adsorption for the investigation of the shape selective properties and effective pore sizes of zeolites. (C) 2012 Elsevier Inc. All rights reserved.