- Abstract The microstructural evolution in the nucleation stage of a synthesis reaction of ZSM-5 zeolite was studied, with particular emphasis on the role of the organic cation, TPA + (tetrapropylammonium). Direct observation of the microstructure was achieved by cryo-transmission electron microscopy (cryo-TEM). The quantitative evaluation of the structural units was obtained by small-angle X-ray scattering (SAXS) measurements. In the presence of the organic cation TPA + , we found globular structural units 5 nm in diameter that aggregate to elongated bodies 44 nm long. The globular structural units were found in reaction mixtures with or without the organic template TPA-OH, as long as the pH of the initial solution was kept above 11.6. Without TPA + , aggregation to cylindrical particles was not observed after 2 h of heating, and no ZSM-5 crystallinity was attained at the end of the reaction (after 8 d). These results suggest that the zeolite ZSM-5 building blocks are globular structural units, 5 nm in diameter, containing silica, alumina, organic cation, and water, which fuse together to produce elongated aggregates that may compose the final unit cell. It is concluded that the globular structural unit is a cluster of tetrapods similar to those found in the final ZSM-5 crystals.