In this paper, the formation of Langmuir-Blodgett films of poly(p-acryloylaminophenylmethylphosphonic) acid polymers, with general formula (C10H12NPO4)n are reported. The Langmuir-Blodgett (LB) technique was used for building ordered nanostructures in molecular assemblies of these polymers, which were able to form stable films. At the air-water interface, these polymers (with low and high molecular weight) formed Langmuir (L) monolayers, which were characterized by surface pressure versus molecular area (π-A) isotherms and Brewster´s Angle Microscopy (BAM). Using the LB method, molecular mono and multilayer films of these polymers were prepared and transferred onto glass substrates forming Z-type multilayers, with a transfer ratio close to unity. These LB films were characterized by Atomic Force Microscopy (AFM).