A semiempirical correlation between the optical band gap of binary oxides and the difference of electronegativity between the oxygen and metallic elements (Pauling’s extraionic energy) is proposed. In the frame of the proposed correlation an estimate of the repulsive term in the total lattice energy of ionic oxides is obtained in very good agreement with the existing data. An extension of the correlation to the ternary oxides and hydroxides is proposed by using the concept of average cationic or anionic group electronegativity. The usefulness of the proposed correlation for the in situ characterization of passive films on metals and alloys by photocurrent spectroscopy is illustrated by reporting some preliminary experimental results on Sn and AlTi alloy.