Carbon films obtained by the spray-pyrolysis technique were applied to the construction of electrodes sensitive to dissolved oxygen. Four types of the carbon electrodes were examined: virgin carbon from polyfurfuryl alcohol (A), virgin carbon with a hematin film (B), Fe-modified carbon (C), and Fe-modified carbon covered with a film of hematin (D). The layer of hematin basically played the role of an accumulator of physically adsorbed oxygen. The application of the hematin film yielded carbon electrodes of better stability. Such an electrode exhibited the capability for the very strict two electron reduction of oxygen molecule in the relatively wide range of oxygen concentration in water. Except for electrochemical tests, all types of carbon electrodes (including the hematin covered one) were examined using XP spectroscopy, FT-IR spectroscopy, and SE microscopy.