Ba 2 La 4 Ti 5 O 1 8 crystallizes in the trigonal system (space group R 3 ) with the unit-cell parameters: a = 5.584 (1) 9; c = 41.176 (8) 9; Z = 3.The structure has been solved from single crystal X-ray diffraction data to a final R 1 = 0.0285. Ba and La atoms are twelve-fold coordinated and Ti atoms six-fold coordinated. The structure can be described as consisting of identical perovskite-like blocks, five corner-sharing TiO 6 octahedra thick, separated by layers of vacant octahedra. The distortion of the cation and anion sublattices has been analysed and a Ba/La order has been evidenced.