A capillary electrophoresis (CE) method with ultraviolet/visible (UV-Vis) spectroscopy for iron speciation in lithium ion battery (LIB) electrolytes was developed. The complexation of Fe(2+)with 1,10-phenantroline (o-phen) and of Fe(3+)with ethylenediamine tetraacetic acid (EDTA) revealed effective stabilization of both iron species during sample preparation and CE measurements. For the investigation of small electrolyte volumes from LIB cells, a sample buffer with optimal sample pH was developed to inhibit precipitation of Fe(3+)during complexation of Fe(2+)witho-phen. However, the presence of the conducting salt lithium hexafluorophosphate (LiPF6) in the electrolyte led to the precipitation of the complex [Fe(o-phen)(3)](PF6)(2). Addition of acetonitrile (ACN) to the sample successfully re-dissolved this Fe2+-complex to retain the quantification of both species. Further optimization of the method successfully prevented the oxidation of dissolved Fe(2+)with ambient oxygen during sample preparation, by previously stabilizing the sample with HCl or by working under counterflow of argon. Following dissolution experiments with the positive electrode material LiFePO4(LFP) in LIB electrolytes under dry room conditions at 20 degrees C and 60 degrees C mainly revealed iron dissolution at elevated temperatures due to the formation of acidic electrolyte decomposition products. Despite the primary oxidation state of iron in LFP of +2, both iron species were detected in the electrolytes that derive from oxidation of dissolved Fe(2+)by remaining molecular oxygen in the sample vials during the dissolution experiments.