Abstract Silyl-substituted naphthalene derivatives, tris(1-napthyl)silicon (IV) chloride (1), tris(1-napthyl)silicon (IV) hydroxide (2) and tris(1-napthyl)silicon (IV)-n-butoxide (3) have been structurally characterized by single-crystal X-ray diffraction. The close intermolecular proximity of the naphthyl substituents groups in 1–3 results in a variety of C–H---π intermolecular interactions to form