The mixed-valence complex Fe3O(cyanoacetate)(6)(H2O)(3) (1) has been studied by single-crystal X-ray diffraction analysis at pressures up to 5.3(1) GPa and by (synchrotron) Mossbauer spectroscopy at pressures up to 8(1) GPa. Crystal structure refinements were possible up to 4.0(1) GPa. In this pressure range, 1 undergoes two pressure-induced phase transitions. The first phase transition at around 3 GPa is isosymmetric and involves a 608 rotation of 50% of the cyanoacetate ligands. The second phase transition at around 4 GPa reduces the symmetry from rhombohedral to triclinic. Mossbauer spectra show that the complex becomes partially valence-trapped after the second phase transition. This sluggish pressure-induced valence-trapping is in contrast to the very abrupt valence-trapping observed when compound 1 is cooled from 130 to 120 K at ambient pressure.