A tetrabutylammonium–H₂Ti₄O₉·xH₂O intercalation compound was obtained by a guest exchange reaction between tetrabutylammonium hydroxide and an ethylammonium–H₂Ti₄O₉·xH₂O intercalation compound, and its dispersion state in aqueous and non-aqueous solutions were studied. Spontaneous exfoliation of H₂Ti₄O₉·xH₂O into colloidal nanosheets occurred when the tetrabutylammonium–H₂Ti₄O₉·xH₂O intercalation compound was dispersed in water, methyl alcohol, isopropyl alcohol, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, and propylene carbonate, while exfoliation did not occur in tetrahydrofuran. A tetrabutylammonium–H₂Ti₄O₉·xH₂O film was obtained by a reassembly process by casting the colloidal suspension containing exfoliated nanosheets, while a H₂Ti₄O₉·xH₂O film was directly obtained by electrophoretic deposition. Thermal treatment of the electrophoretically deposited film led to an oriented TiO₂(B) film with the (0k0) planes lying perpendicular to the substrate.