This paper addresses the detailed investigation on the electrochemical activity of TiO2/PVA nanocomposite-modified pencil graphite electrode (TiO2/PVA-PGE) in aqueous KCl medium at room temperature. Herein, we have used ferri/ferrocyanide redox couple as probe molecule and demonstrated the reversibility, surface diffusion ability, stability, and electroactive surface area of TiO2/PVA-PGE. Formation of functional groups, structure, and the morphology of the prepared sample are examined using various characterization techniques. On top of this, the as-modified PGE is used for the first time in the voltammetric detection of potassium ferricyanide in aqueous KCl medium. The developed sensor is sensitive for only ferricyanide molecule and does not show any current response for other interfering compounds such as, ascorbic acid (AA), Uric acid (UA), dopamine (DA), acetaminophen (ACOP), Hydrogen peroxide (H2O2), and 4-nitrophenol (4-NP) within wide linear range of 0.17-33.33 mM with a high order of correlation (0.997) having a detection limit as low as 0.15 mu M. Also high sensitivity of 199.34 mu A mM(-1) cm(-2) for oxidation current is obtained. The finding of present paper gives a very clear and concise understanding towards the role of modification on the surface electrochemistry of any bare/unmodified electrode and shows the ample possibility in the application of the prepared TiO2/PVA nanocomposite-modified electrodes for selective electrochemical sensing of cyanometalic compound in the presence of other electroactive molecules.