The band edge positions of a nitrogen-fixing nanostructured semiconductor thin film are determined both in the dark through spectroelectrochemistry and under irradiation by photovoltage measurements. Both methods afford the same result indicating that the film in addition to the dinitrogen-fixing phase Fe2Ti2O7 also contains titanium dioxide. Thus, both methods enable the analysis of a mixture of semiconducting thin films. For pH 7, values of -0.4 and +1.6 V were estimated for the conduction and valence band edge of the iron titanate film, respectively. A 3-fold photocurrent increase by methanol was observed only when the film was calcined at 600 degrees C but not below or above this temperature; the films calcined at temperatures other than 600 degrees C were also inactive in the photoreduction of dinitrogen. For a matter of comparison, an iron(Ill) oxide film was characterized analogously.