A systematic study into phase formation in the system Na2OLi2OTiO2 has been carried out at subsolidus temperatures, ca. 900–1000 °C. An experimental study of compound formation and phase equilibrium in this ternary system for compositions containing > 50% TiO2 was made. Five ternary phases were encountered; three of them have variable composition. Solid solution called phase A, is centered on Na5.4Li1.6Ti6.5O16.5 (isostructural to Na0.68Ni0.34Ti0.66O2), phase B is centered on Na2Li2Ti6O14 (isostructural to SrLi2Ti6O14), and phase C is based on Na2LiTi8.5O18.5 (isostructural to Na2Fe2Ti6O16). Two ternary compounds were also found with composition: Na5.6Li2.8Ti5.8O15.8 and Na7Li3Ti5O15 (isostructural to Na0.75Fe0.75Ti0.25O2 and Na2.76Li1.24Ti2O6 respectively). The sodium lithium titanate with composition Na2Li2Ti6O14 has been synthesized by solid state reaction at 970 °C. The characterization was made by X-ray powder diffraction technique. The structure of Na2Li2Ti6O14 was solved using X-ray data (CuKα1,2 radiation), which were indexed using space group Cmca (64), with cell parameters a = 16.4749(1), b = 11.2161(1) and c = 11.4654(1). Crystal structure refinement was performed by means of Rietveld method, with the conventional factors Rwp = 19.2; Rexp = 14.40. Na2Li2Ti6O14 phase structure is described as a network of intercalated edge and corner-sharing distorted TiO6 octahedra. Na ions are surrounded by 11 oxygen atoms, while Ti and Li atoms maintain a coordination of 6 and 4, respectively. This arrangement provides tunnels along the z-axis, in which the lithium atoms are located, forming distorted tetrahedra. [Copyright &y& Elsevier]