Fe(CO)2[O2CCH2P(C6H5)2]2 (I) was synthesized from FeSO4·7H2O and Na[O2CCH2P(C6H5)2] under CO pressure. The 18-electron compound has an octahedral coordination sphere around Fe2+. Two diphenylphosphinoacetate ligands are bonded to the iron through the phosphorus atoms and one of the oxygen atoms of the carboxylato groups. Two carbonyl groups and two carboxylato oxygen atoms are in cis positions to each other, while the phosphorus atoms adopt trans positions. The unit cell contains both enantiomers of the chiral octahedral compound.