The structure of orthorhombic rare earth titanates of La 2 TiO 5 and Nd 2 TiO 5 , where Ti cations are in five-fold coordination with oxygen, has been studied at high pressures by X-ray diffraction (XRD), Raman scattering measurements, and quantum mechanical calculations. Both XRD and Raman results indicated two pressure-induced phase transitions during the process. An orthorhombic super cell (a×b×2c) formed at a pressure between 6 and 10GPa, and then transformed to a hexagonal high-pressure phase accompanied by partial decomposition. The hexagonal high-pressure phase is quenchable. Detailed structural analysis indicated that the five-coordinated TiO 5 polyhedra remain during the formation of super cell, but the orthorhombic-to-hexagonal phase transition at high pressures is a reconstructive process, and the five-fold Ti–O coordination increased to more than 6. This phase transition sequence was verified by quantum mechanical calculations.