Layer-by-layer (LBL) self-assembled ultrathin films were prepared via consecutively alternating immersion of substrates into solutions of electron donor, poly(dithiafulvene) (PDF), and electron acceptor, poly(hexanyl viologen) (6-VP). The charge transfer (CT) interaction formed at solid-liquid interfaces between the backbones of the electron acceptor and donor polymers was the driving force of the alternative deposition. The sandwich heterostructure of the LBL film led to electrical anisotropy in the directions parallel and perpendicular to the film surfaces. Incorporation of gold nanoparticles into the LBL films was investigated by reducing gold ions with the PDF layers already deposited on the film surfaces, or depositing PDF-protected gold colloidal solution as the electron donor layers directly. The influence of the gold nanoparticles on the electrical anisotropy of the LBL films was also illustrated in this research. (c) 2006 Wiley Periodicals, Inc.