A human whole blood-chemically modified electrode prepared using graphitized mesoporous carbon and Nafion, as an in-vitro model system, has been studied for the specific interaction of hydrogen peroxide at biased potentials by cyclic volumetric technique. A blood-chemically modified electrode prepared by modifying a few drops of human whole blood with the carbon nanomaterial and Nafion had showed a well-defined redox peak at an apparent standard electrode potentials, E-center dot similar to'- 0.38 V vs Ag/AgCl in N-2 purged pH 7 phosphate buffer solution, similar to an isolated hemoglobin protein redox feature. When the blood modified electrode is exposed with dilute solution of hydrogen peroxide, selective electrochemical reduction behaviour where the heme site redox potential exists was noticed. The electrochemical reduction reaction is found to follow diffusion controlled mechanism. The H2O2 reduction peak current was linear with the concentration in a range of 100 to 800 mu M with a current sensitivity of 0.048 mu A mu M-1. Qualitative cyclic voltammetric patterns of the blood modified electrode in the entire concentration window of H2O2 are same indicating intact biomolecular arrangement of the heme site. Kinetic parameters of the electron-transfer reaction of H2O2 were estimated using rotating disc technique and Michaelis-Menten reaction approaches. The electron-transfer function of the heme in the RBC is not influenced by any other electroactive biochemicals such as glucose, nitrate, ascorbic acid, uric acid and dopamine, except nitrite. As an independent study, the blood-chemically modified electrode has been used as an electrochemical sensor system for the flow injection analysis of H2O2.