Formation of a stable monolayer of polyaniline (EB) at the air-water interface has been obtained, employing N-methylpyrrolidone (NMP) as processing solvent. Surface pressure-mean molecular area isotherm and compressibility of the polyaniline monolayer were studied under different subphase conditions such as the subphase temperature, the subphase pH, and the nature of counterions in the subphase. The mean molecular area found and compressibility results have been interpreted in terms of the rigidity of the polymer chains at the air-water interface. Further, polyaniline monolayers have been transferred onto different substrates and the multilayers were characterized by spectroscopic, electrical, and electrochemical techniques. The Langmuir-Blodgett multilayers were also deposited at different surface pressures. The transfer behavior and the electrochemical characteristics of these films indicate differences in their packing arrangement.