Abstract The crystal structure of a sodium titanium oxide Na2TiO3 obtained by high temperature solid state reaction method was determined from single-crystal X-ray diffraction study. The compound crystallizes in the monoclinic system, space group C2/c, Mr = 141.88, a = 9.885(1), b = 6.4133(8), c = 5.5048(7) Å, β = 115.50(3)º, V = 314.99(7) Å3, Z = 4, Dc = 2.992 g/cm3, λ = 0.71073 Å, μ = 27.80 cm–1, F(000) = 272, T = 295 K, R = 0.0189 and wR = 0.0512 for 30 variables and 370 contributing unique reflections. The three-dimensional structure in Na2TiO3 is constructed by the TiO(1)4O(2) and NaO(1)3O(2)2 groups. The titanium atoms are grouped in the form of trigonal bipyramid and arranged along the c axis by sharing the edges. The structure is compared with other structures of related A2BO3 compounds.