The intercalation of different primary n-alkylamines in the structure of a layered titanate of the lepidocrocite type (H1.07Ti1.73O4) for application in high-temperature solid lubrication is reported. The intercalation process of the amines was explored by means of in situ small-angle X-ray scattering (SAXS), with variations in alkyl chain length (3–12 carbon atoms) and the amine/titanate ratio. The intercalation process was found to be completed within 5 min after mixing of the precursors in water at 80 °C. The topotactic transformation of the layered titanate is driven by an acid–base reaction. The thermal degradation of the modified titanates was investigated by thermogravimetric analysis (TGA), and the chemical changes were investigated by temperature-dependent infrared spectroscopy (DRIFTS). The coefficient of friction of the lubricants was assessed by means of high-temperature pin-on-disc experiments up to 580 °C. The intercalation of amine rendered a deformable layered ceramic upon heating. It was found that the hydrocarbon chain length exerts an influence on the mechanical properties of the titanates, resulting in lower friction forces for lubricants with longer intercalated amine molecules. Films of solid lubricants with longer amine chain lengths showed coefficients of friction as low as 0.01, lower than that of the state-of-the-art material graphite.