A two-step route comprising treatment in sodium aluminate followed by acid washing was developed to introduce secondary mesoporosity in ZSM-5 zeolites with different Si/Al ratios. The parent and treated zeolites were characterized by ICP-OES (solids and filtrates), XRD, TGA, TEM, gas adsorption (N₂ at 77 K and Ar at 87 K), FTIR, and NH₃-TPD. The contact of the zeolite with NaAlO₂ solutions induced mild leaching of framework silicon, viz. desilication. However, the porosity of the resulting samples was mostly blocked by NaAlO₂-derived deposits and Si-containing debris. A subsequent acid washing with HCl or oxalic acid removed the blocking species, largely regaining the native microporosity and further uncovering the extensive intracrystalline mesoporosity generated in the first step. In order to maximize the micro- and mesoporosity in the final zeolites, the conditions of the NaAlO₂ and acid treatments were varied with respect to concentration, temperature, and time. The efficiency of the two-step treatment was remarkable for zeolites with Si/Al = 25 and 40. The mesopore surface area of the hierarchical ZSM-5 was 3-4 times higher than in the parent zeolites, while other intrinsic properties like crystallinity and acidity were largely preserved. The physico-chemical properties of hierarchical ZSM-5 obtained by the two-step route and by conventional desilication in NaOH were compared. Both desilication variants led to equivalent mesopore surface areas, although the two-step route presented a higher solid yield and produced smaller mesopores due to the much lower amount of silicon leached compared to the treatment in sodium hydroxide. Mechanistic and kinetic aspects of silicon dissolution and porosity development in ZSM-5 were discussed on the basis of alkaline treatments in mixtures of NaOH and NaAlO₂.