Phosphonate layer formation on passive iron surface has been investigated by electrochemical and atomic force microscopy techniques. It was found that phosphonate groups bond more strongly to oxide surface, while metallic iron surface is disadvantageous for phosphonate layer formation in aqueous solutions. The rate of anodic dissolution is continually decreasing due to the time-dependent formation of protective phosphonate layer. The kinetics of phosphonate layer formation on passive iron is determined by the potential applied for preceding passive film formation. The size and shape of iron oxide grains depends slightly on the potential of passivation. Changes in morphology due to the phosphonate layer formation have been recorded by AFM.