Two-dimensional polymer films based on an alkanethiol (11-mercaplo-1-undecanol) monolayer modified with tetrachlorosilane, 1,2-bis(trichlorosilyl)ethane, 1,8-octanediol, and/or octyltriclorosilane were fabricated on the surface of a copper electrode. The films were characterized by Fourier transform infrared reflection spectroscopy and contact angle measurement. The protective efficiency of the film was examined by polarization and impedance measurements of the covered electrode in aerated 0.5 M Na2SO4. A markedly high protective efficiency of the film prepared by multistep modification of the 11-mercapto-1-undecanol monolayer with 1,2-bis(trichlorosilyl)ethane, 1,8-octanediol, and octyltrichlorosilane was obtained, being 98.7%, comparable to the value of the most effective film prepared previously Importantly, the time associated with preparing the previous film was significantly reduced.