The redox behavior and surface characterization of LiFePO₄ in aqueous lithium hydroxide (LiOH) electrolyte have been investigated. The objective of this work is to investigate the electrochemical behavior of LiFePO₄ in an aqueous lithium hydroxide electrolyte and its comparison with that in non-aqueous lithium ion electrolytes. Cyclic voltammetry results show that LiFePO₄ undergoes partially reversible oxidation/reduction. The products formed on electrooxidation and subsequent reduction of LiFePO₄ were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS). It is found that lithium extraction from LiFePO₄ occurs during oxidation. The products formed on subsequent reduction consist of LiFePO₄ and Fe₃O₄.