In this work, we have developed a green method for the preparation of para-nitrotoluene through the catalytic nitration of toluene with nitrogen dioxide (NO₂) under the promotion of dioxygen (O₂). The experimental results reveal that the dealumination of Hβ zeolite has a significant effect on the catalysis of the developed NO₂–O₂–acetic anhydride (Ac₂O) system, in which the conversion of toluene is 78.1% and the selectivity to para-nitrotoluene is 71.8%. Furthermore, the nature of different dealuminated catalysts was investigated by nitrogen adsorption–desorption analysis, X-ray diffraction (XRD), Fourier-transform infrared (FT-IR), thermal gravimetric analysis (TGA), inductively coupled plasma (ICP), ammonia temperature-programmed desorption (NH₃-TPD), pyridine adsorbed Fourier-transform infrared (Py-FT-IR), scanning electron microscopy (SEM) and ²⁷Al magic-angle spinning nuclear magnetic resonance (²⁷Al MAS NMR) techniques. The results of characterization indicate that the structure of the Hβ zeolite still remains and that of Al species in the extra-framework is preferentially removed after acid treatment. Based on the combined results of catalytic characterization and DFT calculation, a feasible reaction mechanism of improved para-selectivity in toluene nitration was suggested for the NO₂–O₂–Ac₂O system.