Linear oligoimides of defined structure were assembled into multilayer structures by the Langmuir-Blodgett (LB) method. Self-assembled monolayer films of thiol-terminated oligoimides were prepared by chemisorption on gold. The imide groups can be reduced electrochemically, and cyclic voltammetry was used to examine the complex electrochemistry of the LB films, and the reduction kinetics of the self-assembled films. Spectroelectrochemistry was used to elucidate the reduction process of the LB films. Comparison of the results for isotropic, self-assembled, and LB films is made in terms of the differing film structures and the mobility of the molecules in the films.