The layer formation of phosphonic acids on mica surface as a model system, from aqueous and ethanol solutions has been investigated. The aggregation behavior (critical micelle concentration, cmc) of molecules in the solution phase has been determined by surface tension measurements in order to select the appropriate concentration for the layer formation experiments. Layer formation of self-assembling molecules of alkyl-phosphonic acids has been followed by atomic force microscopy (AFM). Nucleation, growth and coalescence of densely packed islands of phosphonates from ethanol solution have been recorded on mica surface. The structure of islands depends on the length of alkyl-chains. Self-assembly of phosphonates has been also observed from aqueous solution, as presented by octyl-phosphonic acid (OcPA). The height of OcPA islands is 1.46 0.22 nm, which is practically equal with the length of molecule (1.4 nm). This shows that OcPA molecules form monolayer height domains on the mica surface.