Keywords: High-field EPR spectroscopy / Iron / Coordination chemistry / Citrate ligand / Tripodal ligand / Spin crossover High-field electron paramagnetic resonance spectra have been measured for frozen aqueous solutions of Fe III citrate at acidic and neutral pH values. At high fields (up to 12 T) and high frequencies (95, 190 and 285 GHz), fine-structure peaks due to resonance between Kramers doublets (±1/2, ±3/2, ±5/ 2) of an S = 5/2 species can be observed when the experiments are performed at high temperatures. A full-matrix diagonalisation approach has been used to derive the spinHamiltonian parameters for the S = 5/2 spin state. In acidic media (pH = 2), the spacing of the fine structure reveals that the value of the axial zero-field splitting (ZFS) parameter D is −0.12 cm −1 without rhombicity. A small but significant g anisotropy can be observed which depends slightly on the frequency and the temperature (g x = 2.014, g y = 2.014 and