The nature and spectroscopic expression of external surface sites zeolites, in particular ZSM-5, is a long-debated question. Herein, we use three cutting-edge techniques: Fourier-transform infrared spectroscopy (FTIR) with Fourier self-deconvolution (FSD), high magnetic field proton NMR under fast magic-angle spinning (MAS) periodic boundary Density Functional Theory (DFT) calculations to study...