L 2,3 near-edge fine structures of iron in different oxidation states and coordination numbers, measured with a parallel electron energy-loss spectrometer operating at 1.0–1.3 V resolution, show distinct splittings of the white lines. The splittings have been interpreted in terms of a simple atomic approach involving ligand field splitting of the d orbitals. It is shown that Fe(III) fine structure is particularly sensitive to its coordination.