Weak intermolecular interactions play a major role in structure formation of molecular crystals. Trimethoxy(1-naphthyl)silane (1), the first one-component single-crystalline trimethoxysilane, was analyzed by single-crystal X-ray diffraction. Weak intermolecular interactions were studied by Hirshfeld surface analysis along with 2D fingerprint plots. Both C(methyl)-H...C and C(naphthyl)-H...C interactions were found. A C(naphthyl)-H...O hydrogen bond between a silicon-bound methoxy oxygen and an aromatic hydrogen atom was identified to be a crucial structure-forming interaction within the crystal packing. Therefore, the tendency of molecular aryl-substituted methoxysilanes to crystallize seems to be mainly dependent on the balance between accessible C-H...O hydrogen bonds and C-H...pi interactions.