Mesostructured MFI zeolite nanosheets are established to crystallize non-topotactically through a nanolayered silicate intermediate during hydrothermal synthesis. Solid-state 2D NMR analyses, with sensitivity enhanced by dynamic nuclear polarization (DNP), provide direct evidence of shared covalent 29Si-O-29Si bonds between intermediate nanolayered silicate moieties and the crystallizing MFI zeolite nanosheet framework.