Laser-driven shock compression experiments reveal the presence of a phase transition in MgSiO(3) over the pressure-temperature range 300-400 GPa and 10 000-16 000 K, with a positive Clapeyron slope and a volume change of ∼6.3 (±2.0) percent. The observations are most readily interpreted as an abrupt liquid-liquid transition in a silicate composition representative of terrestrial planetary mantles, implying potentially significant consequences for the thermal-chemical evolution of extrasolar planetary interiors. In addition, the present results extend the Hugoniot equation of state of MgSiO(3) single crystal and glass to 950 GPa.