The article presents a detailed study and characterization of the oxide layers on the surface of iron particles of various sizes. Ten iron samples with a size range from a few nm to 50 µm were studied in detail using SEM, TEM, XRD, and TGA analysis. The composition of the multiphase oxide layers on the powder surface was investigated. The main components of the oxide layer were FeO, Fe3O4, and Fe2O3. By the obtained data, a model for the calculation of a multiphase oxide layer thickness on the surface of iron particles was proposed. The proposed model was validated and can be used for the characterization and certification of micro– and nanoscale iron particles.