The association of capacitive charging of the double-layer and a faradic redox reaction is desirable on carbon fiber (CF) when oxygen functional groups or other heteroatoms are present on its surface enhancing its capacitive properties. In this work, a systematic study of carbon fiber produced at three different heat treatment temperatures (HTT) of 1000, 1500, and 2000 °C was performed upon two approaches: middle (chemical) and severe (electrochemical) oxidative treatments. Morphological, structural, and surface chemical changes were investigated by field emission gun-scanning electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electrochemical responses were analyzed by galvanostatic charge/discharge, electrochemical impedance spectroscopy, and cyclic voltammetry. Raman results showed that the electrochemical oxidation promoted structural variation on CF samples independently of their HTT. Concerning the specific capacitance, the results indicated that chemical treatment was more effective for CF1000 than those for CF1500 and CF2000. This behavior may be attributed to higher amount of oxygen on its surface as well as its lower structural ordering. Otherwise, for CF1000, the electrochemical treatment increased its resistivity. However, for CF1500 and CF2000, which present higher graphitization levels and less heteroatom contents, greater capacitance values were observed after their electrochemical oxidative treatment.