A new phase, BaNb6.3(1)Ti3.6(1)O16, has been synthesised. Electron diffraction studies indicate an hexagonal substructure with unit cell parameters a ≈ 8.9 Å and c ≈ 9.5 Å. In some of the ED patterns superstructure reflections are present, indicating a supercell with a = √3 · asub and c = csub. However, X-ray single-crystal diffraction studies of a crystallite yielding reflections corresponding to the supercell revealed it to be monoclinic, with the unit cell parameters a = 26.811(2) Å, b = 15.4798(2) Å, c = 9.414(2) Å, β = γ = 90° and α = 90.0(3)°. The average crystal structure was refined, using the subcell with a = 8.937(2) Å, b = 15.479(2) Å, c = 9.414(2) Å, β = γ = 90° and α = 90.0(3)°, space group Cm11, and Z = 4, to RI = 3.24% and RwI = 3.44%. The structure can be described as an hexagonal close packing layers of Nb6 octahedra, Ba, and O atoms (A1, A2) and layers of O atoms (B1, B2), appearing in the packing sequence: A1B1A2B2. The Nb6 octahedra are found in isolated Nb6O12O6 clusters, and the Ti atoms in Ti3O13 and Ti3O10 units in octahedral and tetrahedral voids formed by O atoms, respectively. The Ti positions were found to be only partly occupied. Microanalysis indicates that some Nb atoms are located in the Ti3 triangles. A model is presented that interprets these not fully occupied Ti3 triangles as a result of a superimposing of three different structures. Two of these consist of two fused Ti3O13 units, forming an Ti6O19 unit, and a Ti3O10 unit, while the third consists of alternating Ti3O13 units.