A full electrochemical investigation of the lithium intercalation processes in a commercially available PAN-based carbon fiber, Toho Tenax IMS65 (unsized and sized) primarily intended to be used in structural lithium-ion batteries, has been performed. In order to extract the electrochemical properties, a specially designed microelectrode system consisting of a single fiber working electrode, lithium-foil counter electrode and well-characterized battery materials were utilized. The properties, for 5 to 100% state-of-charge (SOC), were mainly determined from electrochemical impedance spectroscopy (EIS) measurements by fitting of a physics-based model, and electronic conductivity examination. The study shows excellent mass transport and kinetic properties, especially at high SOCs for this specific carbon fiber compared to other negative electrode materials. Some electrochemical parameters vary depending on sizing, but are too small to affect the actual electrochemical performance. A strong SOC dependence is shown for most electrochemical properties, including the electronic conductivity. (C) 2013 The Electrochemical Society.