Nanocomposites of multiwalled carbon nanotubes (MWNTs) embedded in poly(o-anisidine) (POAS) were synthesized by oxidative polymerization and characterized using a combination of various techniques. The Langmuir monolayer behavior of POAS-carbon nanotubes (CNTs) conducting polymer was investigated at the air-water interface. The Langmuir-Schaefer (LS) films of POAS-MWNTs were prepared at a subphase of pH. A uniform deposition of monolayers was studied by optical and quartz crystal microbalance techniques, respectively. The nature of the anions in electrochemical investigations revealed significant changes in the redox properties of the POAS-MWNTs LS films. The cyclic voltammetric study revealed a highly electrochemical resistive LS film. The photoelectrochemical current transient of POAS-MWNT LS films was investigated in different electrolytic solutions.