Hierarchical zeolites are advanced materials possessing the catalytic and adsorption properties of conventional zeolites while eliminating their transport limitations through the introduction of mesopores. Recent experiments comparing the adsorption in hierarchical self‐pillared pentasils (SPP) and silicalite‐1 (MFI) revealed an interesting crossover in sorbate loading for branched or long‐chain alkanes but not for shorter linear alkanes, but an explanation for this behavior is not readily available through experimental probes due to the complications arising from the presence of multiple adsorption sites. Here we present a molecular simulation study on the adsorption of alkane isomers and show that a multi‐step mechanism, found here for all molecules, is responsible for the observed phenomena.