[CrFe2O(AcO)(6)(TEP)(3)]Cl, (1), and [CrFe2O(AcO)(6)(TMP)(3)]Cl, (2), were prepared by replacing 3 water molecules in the [CrFe2O(AcO)(6)(H2O)(3)]Cl complex with triethyl- and trimethyl-phosphates, respectively. FT-IR spectroscopy confirmed an oxo-centered, carboxylate-bridged, heteronuclear triangular structure for the title compounds. M3O and MO4 units adopted D-3h and D-4h, local symmetry, respectively, and are surrounded by 6 bridging acetates with C-2v local symmetry.