Pencil graphite (PGE), an ultralow-cost and ready-to-use disposable-type electrode, has been used for various electrochemical and electroanalytical applications after its surface anodization (PGE*, * means preanodized surface). Indeed, systematic studies on mechanistic and surface features of PGE* have not yet been explored. Herein, we report anodized pencil graphite as a model system to study molecular level insights into the surface using a scanning electrochemical microscopy (SECM) technique and dopamine (DA) electrocatalytic oxidation reaction as a molecular probe. The as-prepared PGE* showed an appreciable electronic conductivity similar to the edge-plane graphitic sites (EPPG) of the highly pyrolytic graphitic electrode (HOPG) but without any surface deterioration that occurs with HOPG due to the instability of the EPPG. Physicochemical characterizations by FESEM, FTIR, Raman, and XPS techniques revealed a flake-like exfoliated PGE* surface with higher contents of carbon-oxygen especially phenolic/alcoholic functional groups than the PGE surface. Based on the chronocoulometric experiment, the number of functional groups formed on the PGE* was calculated as 10.9 × 10-10 mol cm-2. An independent SECM technique using ferricyanide as a redox probe showed the existence of a heterogeneous surface and exhibited an improved electron transfer activity due to the flake-like graphitic island on the PGE* surface. Investigated DA electrochemical oxidation on PGE* yielded about three times enhancement in the peak current signal and about 200 mV reduction in the oxidation potential over the PGE without any serious surface fouling feature that is related to the intermediate polydopamine formation on the basal-plane graphitic surface of the underlying electrode. As an independent electroanalytical study, a prototype electrochemical sensor using PGE* as a working electrode for instant detection of DA-containing pharmaceutical samples in a 1 mL Eppendorf vial has been demonstrated.