The majority of the potassium titanates described in the literature were synthesized, and their Raman spectra recorded. The identity of the compounds K2TiO3, K2Ti2O5, K2Ti4O9, K2Ti6O13, and K2Ti8O17 was confirmed by x-ray diffraction. Raman spectroscopy was then used to study the hydrolysis, under different conditions, of K2Ti2O5 and of K2Ti4O9. On drying of the hydrolysis products, the following species were found to form: K2(H2O)0.66 Ti8O16(OH)2, K1.33(H2O)0.33Ti4O8.33(OH)0.67, and H2Ti8O17. On ignition at temperatures of 500–600°C these species converted, respectively, to K2Ti8O17, K2Ti6O13, and TiO2(B). Raman spectroscopy was used to establish that (1) K6Ti4O11 consists of a mixture of K2TiO3 and a new compound K4Ti3O8; (2) K2Ti3O7 consists of a mixture of K2Ti2O5 and K2Ti4O9, and (3) K2Ti5O11 consists of a mixture of K2Ti4O9 and K2Ti6O13. The temperature of decomposition and the identity of the products of the thermal decomposition of K2Ti8Ol7, K2Ti4O9, K2Ti2O5, and K4Ti3O8 were determined by Raman spectroscopy. The XRD data of the newly identified compounds are reported.