In the presented paper, we report on electrochemical oxidation of phenol occurring at exfoliated graphite (EG) in alkaline solution. The mechanism of the electrocatalytic reaction of phenol oxidation was modified on adding methanol to the phenol-containing electrolyte. Using the voltammetry method, the influence of methanol additive on cyclic behavior of EG electrode was examined. A particular attention has been paid to the first two cycles when an abrupt decrease in electrocatalytic activity of various electrode materials has been observed. The results obtained showed that in the presence of methanol EG, electrode preserves its electrocatalytic activity for a longer time of phenol oxidation. In the absence of methanol in a phenol/KOH electrolyte, the charge of phenol oxidation peaks decreases sharply on cycling, whereas in the presence of methanol, the observed drop is considerably inhibited. The anodic charge attained for the 15th cycle of phenol oxidation in methanol-admixed electrolyte is the same as that for the third cycle recorded in methanol-free electrolyte. The thermogravimetric analysis (TG), Fourier-transformed infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) data showed that an improved electrocatalytic activity of EG can be accounted for by new chemical composition of oligomer film built on the EG surface with the participation of methanol and/or the products of its oxidation.