We have used a newly developed ab initio constant-pressure molecular dynamics with variable cell shape technique to investigate the zero temperature behaviour of high pressure clinoenstatite (MgSiO 3 -C2/c) from 0 up to 30 GPa. The optimum structure at 8 GPa, as well as structural trends under pressure, compare very well with experimental data. At this pressure, we find noticeable "fluctuations" in the chain configuration which suggests the structure is on the verge of a mechanical instability. Two distinct compressive behaviours then appear: one below and another above 8 GPa. This phenomenon may be related to the observed transition to a lower symmetry P2 1 /c phase which involves a reconfiguration of the silicate chains, and suggests that the C2/c structure at low pressures found here, may be an artifact of the dynamical algorithm which preserves space group in the absence of symmetry breaking fluctuations. Comparison with calculations in other magnesium silicate phases, indicates that the size and shape of the silicate units (isolated and/or linked tetrahedra and octahedra) are generally well described by the local density approximation; however, the weaker linkages provided by the O-Mg-O bonds, are not as well described. This trend suggests that, as in the recently studied case of H 2 O-ice, the structural properties of more inhomogeneous systems, like enstatite, may be improved by using gradientcorrected density functionals.