Two-dimensional (2D) materials, like 2D covalent organic frameworks (COFs), have been attracting increasing research interest. They are usually obtained as polycrystalline powders. Solid-state NMR spectroscopy is capable of delivering structural information about such materials. Previous studies have applied, for example, ¹³C cross-polarization magic angle spinning (CP MAS) NMR experiments to characterize 2D COFs. Herein, we demonstrate the usefulness of high-field and fast-spinning ¹H MAS NMR spectroscopy to resolve and quantify the signals of different ¹H species within 2D COFs, including the edge sites and/or defects. Moreover, ¹H–¹³C heteronuclear correlation (HETCOR) spectroscopy has also been applied and can provide improved resolution to obtain further information about stacking effects as well as edge sites/defects.