A new polymorph of MgSiO3 more stable than the Pbnm -perovskite phase has been identified by first-principles computations. It has the CaIrO3 structure with Cmcm symmetry and consists of SiO3 layers intercalated by eightfold-coordinated Mg ions. High-temperature calculations within the quasiharmonic approximation give a volume change of ∼1.5% and a Clapeyron slope of ∼7.5±0.3 MPa/K at ∼2750 K and ∼125 GPa. These pressure-temperature (P-T) conditions are close to those in which a phase transition in MgSiO3-perovskite has been observed by in situ angle dispersive X-ray diffraction measurements. This transition appears to be associated with the D″ discontinuity. © 2004 Elsevier B.V. All rights reserved.