Crystal structure of the calcium titanate perovskite CaTiO3 was refined by the Rietveld analysis of neutron diffraction data collected over the temperature range of 296 to 1720 K. The orthorhombic Pbnm-tetragonal 14/mcm phase transformation reversibly occurred at 1512 +/- 13 K and the tetragonal 14/mcm-cubic Pm (3) over barm transition was reversibly observed at 1635 +/- 2 K. The structural phase transitions are characterized by the tilt of the TiO6 octahedron. The tilt systems of the Pbnm, 14/mcm, and Pm (3) over barm CaTiO3 are phi(0)(x)phi(0)(y)phi(+)(z) (phi(-)(x) = phi(-)(y)) phi(0)(x)phi(0)(y)phi(-)(z) and phi(0)(x)phi(0)(y)phi(0)(z), respectively. Here the phi(-)(x), phi(+)(z) and phi(0)(x) stand for the out-of-phase tilt angle of TiO6 octahedron along x axis, the in-phase octahedral tilt angle along z axis, and no octahedral tilting along x axis, respectively. All the tilt angles, phi(-)(x), phi(+)(z) and phi(-)(z) decreased with increasing temperature where the critical exponents were about 0.25. The phi(-)(z) and phi(-)(y) of the orthorhombic structure decreased discontinuously to phi(-)(z) of the tetragonal structure or 0 degrees through the Pbnm-14/mcm transition. The tilt angle, the unit-cell parameters and unit-cell volume discontinuously changed at the Pbnm-14/mcm transition temperature, indicating the first-order nature. The increase of the cell volume in the Pbnm-14/mcm transition was 0.088 vol.% In contrast, the unit-cell volume continuously increased and the tilt angle phi(-)(z) continuously decreased with increasing temperature and became 0 degrees at the 14/mcm-Pm (3) over barm transition temperature, indicating a continuous nature of the transformation. The Pbnm-14/mcm and 14/mcm-Pm (3) over barm phase transitions are induced by the tilting of TiO6 octahedra, indicating the displacive nature of the transitions. The larger thermal motion of O2 atom in 14/mcm CaTiO3 indicates the larger positional disorder of O2 atom, which is consistent with the tilt system phi(0)(x)phi(0)(y)phi(-)(z). (C) 2008 Elsevier B.V. All rights reserved.