Langmuir-type films of poly(5-amino-1-naphthol) conductive polymer were formed at the air/water interface. The surface pressure versus molecular area isotherms of the polymeric layers showed a high tendency to aggregate and non-monomolecular behavior on the water surface. Langmuir–Blodgett (LB) and Langmuir–Schaefer (LS) procedures have been successfully used to transfer the Langmuir films of this polymer onto hydrophilic silicon substrates. Atomic force microscopy images showed that the films obtained by the LS method have much better quality than those obtained by the LB one. In particular, we have obtained uniform and smooth LS films covering practically all the substrate, while the LB films showed rather aggregated material, only partially covering the substrate.