Using in situ high-pressure x-ray diffraction and ab initio techniques, a high-pressure structure of LiTaO3 has been determined to be an orthorhombic phase with the space group Pnma. At ambient temperature, the transition pressure from the R3c phase (the ordinary phase at ambient pressure and temperature) to the Pnma phase is about 33.0 GPa and the phase transition is reversible. This phase transition can be reproduced qualitatively by ab initio calculations, but with a lower transition pressure of 19.9 GPa. The equation of state of LiTaO3 is also reported.