Hierarchical ZSM-5 catalysts with different Si/Al ratios (20, 60 and 100) were hydrothermally synthesized. The prepared samples were studied by several techniques, including X-ray diffraction (XRD), X-ray fluorescence (XRF) analysis, Fourier transform infrared (FTIR) spectroscopy, N2 adsorption–desorption, high resolution transmission electron microscopy (HR-TEM), high resolution scanning electron microscopy (HR-SEM), and differential scanning calorimetry (DSC) technique. The average crystallite size and crystallinity decreases with increasing Si/Al ratio, which is confirmed by XRD. FTIR analysis further confirms the formation of ZSM-5 by the presence of characteristic bending, stretching and framework vibration. The HR-TEM images showed that all the samples having disc-like nanostructures are assembled by many primary nanocrystals. The as-synthesized ZSM-5 zeolites are thermally stable, which is confirmed by DSC. The catalytic activity of ZSM-5 zeolites was evaluated in the selective oxidation of styrene using tertiary-butyl hydroperoxide (TBHP) as the oxidant. Among the catalysts, ZSM-5(60) catalyst showed significantly higher yield of benzaldehyde at optimum conditions. The catalyst was recovered and recycled three times without a significant loss in activity and selectivity. © 2016, Springer Science+Business Media New York.