Crystal structures and structural changes of the compound La0.68(Ti0.95Al0.05)O3 have been studied using neutron powder diffraction data and the Rietveld method in the temperature range from 25° to 592°C. The Rietveld profile‐fitting analyses of the neutron data and the synchrotron diffraction profile revealed that the crystal symmetry of the low‐temperature phase of La0.68(Ti0.95Al0.05)O3 is orthorhombic Cmmm (2ap× 2ap× 2ap; p: pseudo‐cubic perovskite). The unit‐cell and structural parameters were successfully refined with the orthorhombic Cmmm for the intensity data measured at 25°, 182°, and 286°C, and with the tetragonal P4/mmm (ap×ap× 2ap) for intensity data obtained at 388° and 592°C. The P4/mmm‐to‐Cmmm phase transition was found to be induced by tilting of the (TiAl)O6 octahedron. The tilt angle decreased with increasing temperature, reaching 0° at the Cmmm–P4/mmm transition temperature.