Langmuir–Schaefer (LS) films of composite poly(ortho-anisidine) (POAS) and tri-(2,4-di-t-amylphenoxy)-(8-quinolinolyl) copper phthalocyanine (CuPc) were fabricated, and characterized by UV–VIS absorption spectroscopy, quartz crystal microbalance (QCM), electrochemical, in situ spectro-electrochemical techniques, respectively. Surface pressure–area isotherm of composite system showed stable Langmuir films at air–water interface. The uniform deposition of composite monolayers were verified by optical absorption, QCM and cyclic voltammetric measurements. The effects of doping on composite LS films were discussed. Cyclic voltammograms of POAS, CuPc and POAS/CuPc composite systems were also compared. The redox switching response time and diffusion coefficient of such composite LS films were estimated by electrochemical surveying. The photoelectrochemical current transient response of composite LS films was measured at length.